| 5. Round | 25/09/1999 | RCD Mallorca | - | Athletic Club | 2:1 |  |
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| 6. Round | 02/10/1999 | Athletic Club | - | Deportivo La Coruña | 2:3 |  |
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| 7. Round | 11/10/1999 | Málaga CF | - | Athletic Club | 3:4 | ||||
| 8. Round | 15/10/1999 | Athletic Club | - | Valencia CF | 1:0 | |
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| 21. Round | 22/01/2000 | Athletic Club | - | Real Valladolid | 1:0 | ||||
| 23. Round | 05/02/2000 | Athletic Club | - | CD Numancia | 2:1 | ||||
| 25. Round | 18/02/2000 | Deportivo La Coruña | - | Athletic Club | 2:0 | ||||
| 27. Round | 03/03/2000 | Valencia CF | - | Athletic Club | 2:0 | ||||
| 28. Round | 10/03/2000 | Athletic Club | - | FC Barcelona | 0:4 | |
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| 34. Round | 21/04/2000 | Athletic Club | - | RC Celta | 1:0 | ||||
| 35. Round | 29/04/2000 | Real Zaragoza | - | Athletic Club | 0:0 | ||||
| 36. Round | 06/05/2000 | Athletic Club | - | Racing Santander | 2:2 |
Spain