| 1. Round | 29/08/2010 | Real Sociedad | - | Villarreal CF | 1:0 | ||||
| 2. Round | 12/09/2010 | Villarreal CF | - | Espanyol Barcelona | 4:0 | ||||
| 3. Round | 19/09/2010 | Levante UD | - | Villarreal CF | 1:2 | ||||
| 6. Round | 03/10/2010 | Villarreal CF | - | Racing Santander | 2:0 | ||||
| 7. Round | 18/10/2010 | Hércules CF | - | Villarreal CF | 2:2 | ||||
| 10. Round | 07/11/2010 | Villarreal CF | - | Athletic Club | 4:1 |  |
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| 11. Round | 13/11/2010 | FC Barcelona | - | Villarreal CF | 3:1 | ||||
| 15. Round | 11/12/2010 | Getafe CF | - | Villarreal CF | 1:0 | ||||
| 17. Round | 03/01/2011 | Villarreal CF | - | UD Almería | 2:0 |
Ecuador