| 5. Round | 03/10/2021 | Real Sociedad [Women] | - | Villarreal CF [Women] | 4:0 |  |
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| 6. Round | 10/11/2021 | Villarreal CF [Women] | - | UDG Tenerife Sur [Women] | 0:2 | ||||
| 17. Round | 12/01/2022 | Villarreal CF [Women] | - | Atlético Madrid [Women] | 0:5 | ||||
| 18. Round | 15/01/2022 | Madrid CFF [Women] | - | Villarreal CF [Women] | 2:4 | ||||
| 19. Round | 29/01/2022 | Villarreal CF [Women] | - | Real Sociedad [Women] | 1:4 | ||||
| 20. Round | 02/02/2022 | Sevilla FC [Women] | - | Villarreal CF [Women] | 0:3 | |
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| 23. Round | 20/03/2022 | Villarreal CF [Women] | - | Levante UD [Women] | 0:2 | ||||
| 25. Round | 26/03/2022 | Villarreal CF [Women] | - | Athletic Club [Women] | 1:1 | ||||
| 24. Round | 30/03/2022 | Valencia CF [Women] | - | Villarreal CF [Women] | 2:1 | ||||
| 26. Round | 02/04/2022 | FC Barcelona [Women] | - | Villarreal CF [Women] | 6:1 | ||||
| 27. Round | 17/04/2022 | Villarreal CF [Women] | - | Sporting de Huelva [Women] | 1:1 | ||||
| 28. Round | 01/05/2022 | SD Eibar [Women] | - | Villarreal CF [Women] | 1:1 | ||||
| 29. Round | 08/05/2022 | Villarreal CF [Women] | - | Real Betis [Women] | 2:0 | ||||
| 30. Round | 15/05/2022 | Real Madrid [Women] | - | Villarreal CF [Women] | 1:0 |
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