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Pinnacle West Capital Corp., et al. – ‘10-K’ for 12/31/20 – ‘EX-101.DEF’

On:  Wednesday, 2/24/21, at 8:32am ET   ·   For:  12/31/20   ·   Accession #:  764622-21-13   ·   File #s:  1-04473, 1-08962

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  As Of               Filer                 Filing    For·On·As Docs:Size

 2/24/21  Pinnacle West Capital Corp.       10-K       12/31/20  144:26M
          Arizona Public Service Co.

Annual Report   —   Form 10-K
Filing Table of Contents

Document/Exhibit                   Description                      Pages   Size 

 1: 10-K        Annual Report                                       HTML   3.25M 
 2: EX-4.9      Instrument Defining the Rights of Security Holders  HTML     63K 
 3: EX-10.4.4   Material Contract                                   HTML     51K 
 4: EX-10.4.5A  Material Contract                                   HTML     47K 
 5: EX-10.4.5B  Material Contract                                   HTML     45K 
 6: EX-10.4.6   Material Contract                                   HTML     58K 
 7: EX-10.4.7   Material Contract                                   HTML     52K 
 8: EX-10.4.8   Material Contract                                   HTML     51K 
 9: EX-10.6.4   Material Contract                                   HTML     40K 
10: EX-10.6.5K  Material Contract                                   HTML     77K 
11: EX-10.6.5L  Material Contract                                   HTML     77K 
12: EX-21.1     Subsidiaries List                                   HTML     37K 
13: EX-23.1     Consent of Expert or Counsel                        HTML     37K 
14: EX-23.2     Consent of Expert or Counsel                        HTML     37K 
15: EX-31.1     Certification -- §302 - SOA'02                      HTML     43K 
16: EX-31.2     Certification -- §302 - SOA'02                      HTML     43K 
17: EX-31.3     Certification -- §302 - SOA'02                      HTML     43K 
18: EX-31.4     Certification -- §302 - SOA'02                      HTML     43K 
19: EX-32.1     Certification -- §906 - SOA'02                      HTML     41K 
20: EX-32.2     Certification -- §906 - SOA'02                      HTML     41K 
27: R1          Cover Page                                          HTML    115K 
28: R2          Consolidated Statements of Income                   HTML    136K 
29: R3          Consolidated Statements of Comprehensive Income     HTML     74K 
30: R4          Consolidated Statements of Comprehensive Income     HTML     46K 
                (Parenthetical)                                                  
31: R5          Consolidated Balance Sheets                         HTML    254K 
32: R6          Consolidated Balance Sheets (Parenthetical)         HTML     56K 
33: R7          Consolidated Statements of Cash Flows               HTML    165K 
34: R8          Consolidated Statements of Changes in Equity        HTML    129K 
35: R9          Consolidated Statements of Changes in Equity        HTML     39K 
                (Parenthetical)                                                  
36: R10         Summary of Significant Accounting Policies          HTML    123K 
37: R11         Revenue                                             HTML     71K 
38: R12         New Accounting Standards                            HTML     49K 
39: R13         Regulatory Matters                                  HTML    258K 
40: R14         Income Taxes                                        HTML    225K 
41: R15         Lines of Credit and Short-Term Borrowings           HTML     58K 
42: R16         Long-Term Debt and Liquidity Matters                HTML    105K 
43: R17         Retirement Plans and Other Postretirement Benefits  HTML    311K 
44: R18         Leases                                              HTML     87K 
45: R19         Jointly-Owned Facilities                            HTML     87K 
46: R20         Commitments and Contingencies                       HTML     99K 
47: R21         Asset Retirement Obligations                        HTML     50K 
48: R22         Fair Value Measurements                             HTML    159K 
49: R23         Earnings Per Share                                  HTML     54K 
50: R24         Stock-Based Compensation                            HTML     75K 
51: R25         Derivative Accounting                               HTML    121K 
52: R26         Other Income and Other Expense                      HTML     80K 
53: R27         Palo Verde Sale Leaseback Variable Interest         HTML     48K 
                Entities                                                         
54: R28         Investments in Nuclear Decommissioning Trusts and   HTML    108K 
                Other Special Use Funds                                          
55: R29         Changes in Accumulated Other Comprehensive Loss     HTML     77K 
56: R30         Schedule I - Condensed Financial Information of     HTML    148K 
                Registrant                                                       
57: R31         Summary of Significant Accounting Policies          HTML    141K 
                (Policies)                                                       
58: R32         Summary of Significant Accounting Policies          HTML     80K 
                (Tables)                                                         
59: R33         Revenue (Tables)                                    HTML     64K 
60: R34         Regulatory Matters (Tables)                         HTML    162K 
61: R35         Income Taxes (Tables)                               HTML    224K 
62: R36         Lines of Credit and Short-Term Borrowings (Tables)  HTML     54K 
63: R37         Long-Term Debt and Liquidity Matters (Tables)       HTML    103K 
64: R38         Retirement Plans and Other Postretirement Benefits  HTML    304K 
                (Tables)                                                         
65: R39         Leases (Tables)                                     HTML     85K 
66: R40         Jointly-Owned Facilities (Tables)                   HTML     88K 
67: R41         Commitments and Contingencies (Tables)              HTML     55K 
68: R42         Asset Retirement Obligations (Tables)               HTML     48K 
69: R43         Fair Value Measurements (Tables)                    HTML    139K 
70: R44         Earnings Per Share (Tables)                         HTML     54K 
71: R45         Stock-Based Compensation (Tables)                   HTML     92K 
72: R46         Derivative Accounting (Tables)                      HTML    168K 
73: R47         Other Income and Other Expense (Tables)             HTML     79K 
74: R48         Palo Verde Sale Leaseback Variable Interest         HTML     47K 
                Entities (Tables)                                                
75: R49         Investments in Nuclear Decommissioning Trusts and   HTML    107K 
                Other Special Use Funds (Tables)                                 
76: R50         Changes in Accumulated Other Comprehensive Loss     HTML     76K 
                (Tables)                                                         
77: R51         Summary of Significant Accounting Policies -        HTML    121K 
                Additional Information (Details)                                 
78: R52         Summary of Significant Accounting Policies -        HTML     66K 
                Summary of Property, Plant and Equipment (Details)               
79: R53         Summary of Significant Accounting Policies -        HTML     62K 
                Supplemental Cash Flow Information (Details)                     
80: R54         Revenue - Sources of Revenue (Details)              HTML     55K 
81: R55         Revenue - Additional Information (Details)          HTML     52K 
82: R56         Revenue - Allowance for Doubtful Accounts           HTML     45K 
                (Details)                                                        
83: R57         Regulatory Matters - Regulatory Matters - COVID-19  HTML     79K 
                (Details)                                                        
84: R58         Regulatory Matters - Retail Rate Case Filing        HTML    136K 
                (Details)                                                        
85: R59         Regulatory Matters - Capital Structure and Costs    HTML     52K 
                of Capital (Details)                                             
86: R60         Regulatory Matters - Additional Information         HTML    285K 
                (Details)                                                        
87: R61         Regulatory Matters - Deferred Fuel and Purchased    HTML     50K 
                Power Regulatory Asset (Details)                                 
88: R62         Regulatory Matters - Four Corners, Cholla and       HTML     51K 
                Navajo Plant (Details)                                           
89: R63         Regulatory Matters - Schedule of Regulatory Assets  HTML     96K 
                (Details)                                                        
90: R64         Regulatory Matters - Schedule of Regulatory         HTML     96K 
                Liabilities (Details)                                            
91: R65         Income Taxes - Additional Information (Details)     HTML     62K 
92: R66         Income Taxes - Reconciliation of Unrecognized Tax   HTML     59K 
                Benefits (Details)                                               
93: R67         Income Taxes - Summary of Unrecognized Tax          HTML     47K 
                Benefits (Details)                                               
94: R68         Income Taxes - Components of Income Tax Expense     HTML     64K 
                (Details)                                                        
95: R69         Income Taxes - Effective Tax Rate Reconciliation    HTML     71K 
                (Details)                                                        
96: R70         Income Taxes - Components of Deferred Income Tax    HTML    109K 
                Liability (Details)                                              
97: R71         Lines of Credit and Short-Term Borrowings -         HTML     57K 
                Schedule of Credit Facilities (Details)                          
98: R72         Lines of Credit and Short-Term Borrowings -         HTML    104K 
                Additional Information (Details)                                 
99: R73         Long-Term Debt and Liquidity Matters - Components   HTML    100K 
                of Long-Term Debt (Details)                                      
100: R74         Long-Term Debt and Liquidity Matters - Additional   HTML    116K  
                Information (Details)                                            
101: R75         Long-Term Debt and Liquidity Matters - Future       HTML     61K  
                Principal Payments (Details)                                     
102: R76         Long-Term Debt and Liquidity Matters - Fair Value   HTML     46K  
                of Long-Term Debt (Details)                                      
103: R77         Retirement Plans and Other Postretirement Benefits  HTML     84K  
                - Additional Information (Details)                               
104: R78         Retirement Plans and Other Postretirement Benefits  HTML     66K  
                - Net Periodic Benefit Costs and Portion including               
                Portion Charged to Expense (Details)                             
105: R79         Retirement Plans and Other Postretirement Benefits  HTML     78K  
                - Changes Benefit Obligations and Funded Status                  
                (Details)                                                        
106: R80         Retirement Plans and Other Postretirement Benefits  HTML     49K  
                - Projected Benefit Obligation for Pension Plans                 
                (Details)                                                        
107: R81         Retirement Plans and Other Postretirement Benefits  HTML     56K  
                - Amounts Recognized on the Consolidated Balance                 
                Sheets (Details)                                                 
108: R82         Retirement Plans and Other Postretirement Benefits  HTML     55K  
                - Impact to Accumulated Other Comprehensive Loss                 
                (Details)                                                        
109: R83         Retirement Plans and Other Postretirement Benefits  HTML     80K  
                - Weighted-Average Assumptions for Pensions and                  
                Other Benefits (Details)                                         
110: R84         Retirement Plans and Other Postretirement Benefits  HTML     61K  
                - Asset Allocation (Details)                                     
111: R85         Retirement Plans and Other Postretirement Benefits  HTML    118K  
                - Fair Value of Pinnacle West's Pension Plan                     
                (Details)                                                        
112: R86         Retirement Plans and Other Postretirement Benefits  HTML     55K  
                - Estimated Future Benefit Payments (Details)                    
113: R87         Leases - Additional information (Details)           HTML     61K  
114: R88         Leases - Lease costs (Details)                      HTML     53K  
115: R89         Leases - Maturity of our operating lease            HTML     66K  
                liabilities (Details)                                            
116: R90         Leases - Other additional information related to    HTML     47K  
                operating lease liabilities (Details)                            
117: R91         Jointly-Owned Facilities (Details)                  HTML    102K  
118: R92         Commitments and Contingencies - Palo Verde Nuclear  HTML    119K  
                Generating Station and Contractual Obligations                   
                (Details)                                                        
119: R93         Commitments and Contingencies - Superfund-Related   HTML     48K  
                Matters and Southwest Power Outage (Details)                     
120: R94         Commitments and Contingencies - Environmental       HTML    105K  
                Matters and Financial Assurances (Details)                       
121: R95         Asset Retirement Obligations (Details)              HTML     63K  
122: R96         Fair Value Measurements - Fair Value of Assets and  HTML    122K  
                Liabilities (Details)                                            
123: R97         Fair Value Measurements - Additional Information    HTML     48K  
                (Details)                                                        
124: R98         Earnings Per Share (Details)                        HTML     66K  
125: R99         Stock-Based Compensation - Additional Information   HTML    101K  
                (Details)                                                        
126: R100        Stock-Based Compensation - Summary of Restricted    HTML     49K  
                Stock, Stock Grants, Stock Units and Performance                 
                Shares (Details)                                                 
127: R101        Stock-Based Compensation - Status of Nonvested      HTML     78K  
                Restricted Stock, Stock Grants, Stock Units and                  
                Performance Shares (Details)                                     
128: R102        Derivative Accounting - Additional Information      HTML     56K  
                (Details)                                                        
129: R103        Derivative Accounting - Outstanding Gross Notional  HTML     42K  
                Amounts Outstanding (Details)                                    
130: R104        Derivative Accounting - Gains and Losses from       HTML     55K  
                Derivative Instruments (Details)                                 
131: R105        Derivative Accounting - Derivative Instruments in   HTML     97K  
                the Balance Sheet (Details)                                      
132: R106        Derivative Accounting - Credit Risk and Related     HTML     45K  
                Contingent Features (Details)                                    
133: R107        Other Income and Other Expense (Details)            HTML     79K  
134: R108        Palo Verde Sale Leaseback Variable Interest         HTML     70K  
                Entities (Details)                                               
135: R109        Palo Verde Sale Leaseback Variable Interest         HTML     51K  
                Entities - Schedule of VIEs (Details)                            
136: R110        Investments in Nuclear Decommissioning Trusts and   HTML    133K  
                Other Special Use Funds (Details)                                
137: R111        Changes in Accumulated Other Comprehensive Loss     HTML     73K  
                (Details)                                                        
138: R112        SCHEDULE I - CONDENSED FINANCIAL INFORMATION OF     HTML     77K  
                REGISTRANT - Comprehensive Income (Details)                      
139: R113        SCHEDULE I - CONDENSED FINANCIAL INFORMATION OF     HTML    154K  
                REGISTRANT - Balance Sheets (Details)                            
140: R114        SCHEDULE I - CONDENSED FINANCIAL INFORMATION OF     HTML    117K  
                REGISTRANT - Cash Flows (Details)                                
142: XML         IDEA XML File -- Filing Summary                      XML    254K  
26: XML         XBRL Instance -- pnw-20201231_htm                    XML   7.07M 
141: EXCEL       IDEA Workbook of Financial Reports                  XLSX    234K  
22: EX-101.CAL  XBRL Calculations -- pnw-20201231_cal                XML    507K 
23: EX-101.DEF  XBRL Definitions -- pnw-20201231_def                 XML   2.30M 
24: EX-101.LAB  XBRL Labels -- pnw-20201231_lab                      XML   3.87M 
25: EX-101.PRE  XBRL Presentations -- pnw-20201231_pre               XML   2.51M 
21: EX-101.SCH  XBRL Schema -- pnw-20201231                          XSD    465K 
143: JSON        XBRL Instance as JSON Data -- MetaLinks              763±  1.19M  
144: ZIP         XBRL Zipped Folder -- 0000764622-21-000013-xbrl      Zip   1.24M  


‘EX-101.DEF’   —   XBRL Definitions — pnw-20201231_def


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11 Subsequent Filings that Reference this Filing

  As Of               Filer                 Filing    For·On·As Docs:Size             Issuer                      Filing Agent

 2/27/24  Pinnacle West Capital Corp.       10-K       12/31/23  147:25M
 6/28/23  Arizona Public Service Co.        424B2                  2:578K                                   Toppan Merrill/FA
 6/27/23  Arizona Public Service Co.        424B3                  1:558K                                   Toppan Merrill/FA
 2/27/23  Pinnacle West Capital Corp.       10-K       12/31/22  146:28M
11/07/22  Arizona Public Service Co.        424B2                  2:573K                                   Toppan Merrill/FA
11/04/22  Arizona Public Service Co.        424B3                  1:531K                                   Toppan Merrill/FA
 2/25/22  Pinnacle West Capital Corp.       10-K       12/31/21  150:28M
 8/12/21  Arizona Public Service Co.        424B2                  1:540K                                   Toppan Merrill/FA
 8/11/21  Arizona Public Service Co.        424B3                  1:539K                                   Toppan Merrill/FA
 6/03/21  Pinnacle West Capital Corp.       S-8         6/03/21    4:138K
 3/04/21  Pinnacle West Capital Corp.       S-3ASR      3/04/21   12:633K                                   Toppan Merrill/FA


74 Previous Filings that this Filing References

  As Of               Filer                 Filing    For·On·As Docs:Size             Issuer                      Filing Agent

 9/11/20  Pinnacle West Capital Corp.       8-K:9       9/08/20   17:728K
 6/16/20  Pinnacle West Capital Corp.       8-K:9       6/10/20   17:610K
 5/22/20  Pinnacle West Capital Corp.       8-K:9       5/19/20   17:706K
 5/08/20  Pinnacle West Capital Corp.       10-Q        3/31/20   90:14M
 2/25/20  Pinnacle West Capital Corp.       8-K:5,9     2/19/20   13:633K
 2/21/20  Pinnacle West Capital Corp.       10-K       12/31/19  144:30M
11/20/19  Pinnacle West Capital Corp.       8-K:9      11/18/19   17:701K
 8/16/19  Pinnacle West Capital Corp.       8-K:9       8/12/19   17:700K
 5/01/19  Pinnacle West Capital Corp.       10-Q        3/31/19   92:14M
 2/28/19  Pinnacle West Capital Corp.       8-K:9       2/26/19    6:405K
 8/03/18  Pinnacle West Capital Corp.       10-Q        6/30/18   91:21M
 2/23/18  Pinnacle West Capital Corp.       10-K12/31/17  138:27M
 9/11/17  Pinnacle West Capital Corp.       8-K:9       9/06/17    6:415K
 8/03/17  Pinnacle West Capital Corp.       10-Q        6/30/17   85:13M
 6/20/17  Pinnacle West Capital Corp.       8-K:8,9     6/20/17    2:717K
 5/02/17  Pinnacle West Capital Corp.       10-Q        3/31/17   81:16M
 3/31/17  Pinnacle West Capital Corp.       DEF 14A     5/17/17    1:4.3M                                   Toppan Merrill-FA
 2/24/17  Pinnacle West Capital Corp.       10-K12/31/16  138:27M
 9/20/16  Pinnacle West Capital Corp.       8-K:9       9/15/16    6:412K
 5/06/16  Pinnacle West Capital Corp.       8-K:9       5/03/16    6:488K                                   Toppan Merrill/FA
 2/19/16  Pinnacle West Capital Corp.       10-K       12/31/15  137:27M
11/06/15  Pinnacle West Capital Corp.       8-K:9      11/03/15    6:415K
10/30/15  Pinnacle West Capital Corp.       10-Q        9/30/15   87:13M
 5/19/15  Pinnacle West Capital Corp.       8-K:9       5/14/15    6:406K
 2/20/15  Pinnacle West Capital Corp.       10-K12/31/14  146:38M
 7/31/14  Pinnacle West Capital Corp.       10-Q        6/30/14   98:26M                                    Toppan Merrill/FA
 5/02/14  Pinnacle West Capital Corp.       10-Q        3/31/14   94:19M                                    Toppan Merrill/FA
 2/21/14  Pinnacle West Capital Corp.       10-K12/31/13  148:38M                                    Toppan Merrill/FA
 2/22/13  Arizona Public Service Co.        10-K12/31/12  140:39M                                    Toppan Merrill/FA
 5/22/12  Arizona Public Service Co.        8-K:5,9     5/16/12    3:147K                                   Toppan Merrill/FA
 5/03/12  Arizona Public Service Co.        10-Q        3/31/12   93:19M                                    Toppan Merrill/FA
 3/29/12  Pinnacle West Capital Corp.       DEF 14A     5/16/12    1:2.3M                                   Toppan Merrill-FA
 2/24/12  Arizona Public Service Co.        10-K       12/31/11  143:50M                                    Toppan Merrill/FA
 4/29/11  Arizona Public Service Co.        10-Q        3/31/11   52:5.9M                                   Donnelley … Solutions/FA
 2/18/11  Arizona Public Service Co.        10-K       12/31/10   68:13M                                    Donnelley … Solutions/FA
11/08/10  Arizona Public Service Co.        8-K:1,8,9  11/08/10    3:994K                                   Donnelley … Solutions/FA
 8/03/10  Arizona Public Service Co.        10-Q        6/30/10   49:5.5M                                   Donnelley … Solutions/FA
 5/06/10  Arizona Public Service Co.        10-Q        3/31/10   14:2.1M                                   Donnelley … Solutions/FA
 2/19/10  Arizona Public Service Co.        10-K       12/31/09   19:3.1M                                   Donnelley … Solutions/FA
 5/05/09  Arizona Public Service Co.        10-Q        3/31/09   14:899K                                   RR Donnelley
 2/20/09  Arizona Public Service Co.        10-K       12/31/08   19:2.3M                                   RR Donnelley
11/25/08  Pinnacle West Capital Corp.       S-3ASR     11/25/08    5:271K                                   RR Donnelley
 8/07/08  Pinnacle West Capital Corp.       10-Q        6/30/08   17:900K                                   Bowne - BPX/FA
 2/27/08  Arizona Public Service Co.        10-K       12/31/07   15:1.9M                                   Bowne - BPX/FA
11/06/07  Pinnacle West Capital Corp.       10-Q        9/30/07   14:908K                                   Bowne - BPX/FA
 5/09/07  Arizona Public Service Co.        10-Q        3/31/07   14:741K                                   Bowne - BPX/FA
 4/20/07  Arizona Public Service Co.        8-K:8,9     4/18/07    3:54K                                    RR Donnelley
 4/20/07  Pinnacle West Capital Corp.       DEF 14A     5/23/07    1:757K                                   RR Donnelley
 8/03/06  Arizona Public Service Co.        8-K:9       7/31/06    7:324K                                   Bowne - BPX/FA
 3/13/06  Arizona Public Service Co.        10-K       12/31/05   25:3.1M                                   Bowne - BPX/FA
 8/22/05  Arizona Public Service Co.        8-K:9       8/17/05    4:102K                                   Bowne - BPX/FA
 8/09/05  Arizona Public Service Co.        10-Q        6/30/05   15:1.2M                                   Bowne - BPX/FA
 3/16/05  Arizona Public Service Co.        10-K12/31/04   28:2.5M                                   Bowne - BPX/FA
 8/09/04  Pinnacle West Capital Corp.       8-K:7       6/23/04    2:78K                                    Bowne - BPX/FA
 3/15/04  Pinnacle West Capital Corp.       10-K       12/31/03   16:1.8M                                   Bowne - BPX/FA
 5/15/03  Pinnacle West Capital Corp.       10-Q        3/31/03    9:364K                                   Imperial Fin’l … Corp/FA
 5/09/03  Arizona Public Service Co.        8-K:7       5/07/03    7:139K                                   Imperial Fin’l … Corp/FA
 5/15/02  Pinnacle West Capital Corp.       10-Q        3/31/02    7:161K                                   Imperial Fin’l … Corp/FA
 3/14/01  Pinnacle West Capital Corp.       10-K       12/31/00   12:288K                                   Imperial Fin’l … Corp/FA
12/21/00  Pinnacle West Capital Corp.       S-3                    9:512K                                   Imperial Fin’l … Corp/FA
 8/14/00  Pinnacle West Capital Corp.       10-Q        6/30/00    3:92K                                    Imperial Fin’l … Corp/FA
 3/30/00  Pinnacle West Capital Corp.       10-K       12/31/99   21:332K                                   Imperial Fin’l … Corp/FA
11/15/99  Arizona Public Service Co.        10-Q        9/30/99    4:376K                                   Imperial Fin’l … Corp/FA
 6/26/98  Arizona Public Service Co.        8-K:5,7     5/19/98    3:34K                                    Imperial Fin’l … Corp/FA
 5/15/98  Pinnacle West Capital Corp.       10-Q        3/31/98    2:49K                                    Imperial Fin’l … Corp/FA
 1/16/98  Arizona Public Service Co.        8-K:7       1/13/98    6:280K                                   Imperial Fin’l … Corp/FA
 3/28/97  Arizona Public Service Co.        10-K405    12/31/96   13:337K                                   Imperial Fin’l … Corp/FA
11/22/96  Arizona Public Service Co.        8-K:7      11/19/96    7:507K                                   Imperial Fin’l … Corp/FA
 8/09/96  Arizona Public Service Co.        10-Q        6/30/96    4:50K                                    Imperial Fin’l … Corp/FA
 3/29/96  Arizona Public Service Co.        10-K405    12/31/95   15:379K                                   Imperial Fin’l … Corp/FA
 3/30/95  Arizona Public Service Co.        10-K405    12/31/94   14:361K                                   Imperial Fin’l … Corp/FA
 1/11/95  Arizona Public Service Co.        8-K:7       1/01/95    7:295K                                   Imperial Fin’l … Corp/FA
11/10/94  Arizona Public Service Co.        10-Q        9/30/94    5:52K                                    Imperial Fin’l … Corp/FA
 3/30/94  Arizona Public Service Co.        10-K       12/31/93   14:453K                                   Imperial Fin’l … Corp/FA
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