| 1. Round | 13/09/2020 | Villarreal CF | - | SD Huesca | 1:1 | ||||
| 2. Round | 19/09/2020 | Villarreal CF | - | SD Eibar | 2:1 | ||||
| 3. Round | 27/09/2020 | FC Barcelona | - | Villarreal CF | 4:0 | ||||
| 4. Round | 30/09/2020 | Villarreal CF | - | CD Alavés | 3:1 | ||||
| 5. Round | 03/10/2020 | Atlético Madrid | - | Villarreal CF | 0:0 | ||||
| 6. Round | 18/10/2020 | Villarreal CF | - | Valencia CF | 2:1 |  |
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| 7. Round | 25/10/2020 | Cádiz CF | - | Villarreal CF | 0:0 | ||||
| 8. Round | 02/11/2020 | Villarreal CF | - | Real Valladolid | 2:0 | ||||
| 9. Round | 08/11/2020 | Getafe CF | - | Villarreal CF | 1:3 | ||||
| 10. Round | 21/11/2020 | Villarreal CF | - | Real Madrid | 1:1 | ||||
| 11. Round | 29/11/2020 | Real Sociedad | - | Villarreal CF | 1:1 | ||||
| 12. Round | 06/12/2020 | Villarreal CF | - | Elche CF | 0:0 | ||||
| 13. Round | 13/12/2020 | Real Betis | - | Villarreal CF | 1:1 |
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