| 6. Round | 18/09/2022 | Villarreal CF | - | Sevilla FC | 1:1 | ||||
| 7. Round | 01/10/2022 | Cádiz CF | - | Villarreal CF | 0:0 | ||||
| 8. Round | 09/10/2022 | Real Sociedad | - | Villarreal CF | 1:0 | ||||
| 9. Round | 17/10/2022 | Villarreal CF | - | CA Osasuna | 2:0 |  |
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| 10. Round | 20/10/2022 | FC Barcelona | - | Villarreal CF | 3:0 | ||||
| 11. Round | 23/10/2022 | Villarreal CF | - | UD Almería | 2:1 | ||||
| 12. Round | 30/10/2022 | Athletic Club | - | Villarreal CF | 1:0 | ||||
| 13. Round | 06/11/2022 | Villarreal CF | - | RCD Mallorca | 0:2 | ||||
| 14. Round | 09/11/2022 | Espanyol Barcelona | - | Villarreal CF | 0:1 | ||||
| 16. Round | 07/01/2023 | Villarreal CF | - | Real Madrid | 2:1 |
Nigeria
