| 1. Round | 16/08/2021 | Villarreal CF | - | Granada CF | 0:0 |  |
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| 2. Round | 21/08/2021 | Espanyol Barcelona | - | Villarreal CF | 0:0 | ||||
| 3. Round | 29/08/2021 | Atlético Madrid | - | Villarreal CF | 2:2 | |
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| 9. Round | 17/10/2021 | Villarreal CF | - | CA Osasuna | 1:2 |  |
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| 10. Round | 23/10/2021 | Athletic Club | - | Villarreal CF | 2:1 | ||||
| 16. Round | 04/12/2021 | Sevilla FC | - | Villarreal CF | 1:0 | ||||
| 17. Round | 12/12/2021 | Villarreal CF | - | Rayo Vallecano | 2:0 | |
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| 18. Round | 18/12/2021 | Real Sociedad | - | Villarreal CF | 1:3 | |
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| 4. Round | 21/12/2021 | Villarreal CF | - | CD Alavés | 5:2 | |
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| 19. Round | 03/01/2022 | Villarreal CF | - | Levante UD | 5:0 | |
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| 20. Round | 09/01/2022 | Villarreal CF | - | Atlético Madrid | 2:2 | ||||
| 21. Round | 16/01/2022 | Elche CF | - | Villarreal CF | 1:0 | ||||
| 23. Round | 06/02/2022 | Real Betis | - | Villarreal CF | 0:2 | ||||
| 29. Round | 20/03/2022 | Cádiz CF | - | Villarreal CF | 1:0 | ||||
| 30. Round | 02/04/2022 | Levante UD | - | Villarreal CF | 2:0 | ||||
| 31. Round | 09/04/2022 | Villarreal CF | - | Athletic Club | 1:1 | ||||
| 32. Round | 16/04/2022 | Getafe CF | - | Villarreal CF | 1:2 | |
Spain
