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| H | CD Alavés | - | RC Celta | 0:0 (0:0) | ||
| R | RC Celta | - | CD Alavés | 0:1 (0:0) | ||
| H: 24.10.2006 20:45 | R: 09.11.2006 20:45 | Sieger: CD Alavés | ||||
| H | Atlético Madrid | - | Levante UD | 0:1 (0:0) | ||
| R | Levante UD | - | Atlético Madrid | 2:4 (0:0, 0:1, 0:1) i.E. | ||
| H: 24.10.2006 21:00 | R: 13.12.2006 21:00 | Sieger: Atlético Madrid | ||||
| H | Racing Portuense | - | Valencia CF | 1:2 (1:1) | ||
| R | Valencia CF | - | Racing Portuense | 2:0 (2:0) | ||
| H: 25.10.2006 19:00 | R: 08.11.2006 22:00 | Sieger: Valencia CF | ||||
| H | Écija Balompié | - | Real Madrid | 1:1 (0:0) | ||
| R | Real Madrid | - | Écija Balompié | 5:1 (0:0) | ||
| H: 25.10.2006 20:00 | R: 09.11.2006 21:00 | Sieger: Real Madrid | ||||
| H | Peña Sport FC | - | CA Osasuna | 0:0 (0:0) | ||
| R | CA Osasuna | - | Peña Sport FC | 4:0 (1:0) | ||
| H: 25.10.2006 20:30 | R: 08.11.2006 21:00 | Sieger: CA Osasuna | ||||
| H | Gimnástica Segoviana | - | Sevilla FC | 0:1 (0:1) | ||
| R | Sevilla FC | - | Gimnástica Segoviana | 3:0 (2:0) | ||
| H: 25.10.2006 20:30 | R: 08.11.2006 21:00 | Sieger: Sevilla FC | ||||
| H | Deportivo La Coruña | - | Racing Santander | 1:0 (0:0) | ||
| R | Racing Santander | - | Deportivo La Coruña | 1:3 (1:0, 1:0, 1:0) i.E. | ||
| H: 25.10.2006 20:45 | R: 08.11.2006 20:45 | Sieger: Deportivo La Coruña | ||||
| H | Rayo Vallecano | - | Espanyol Barcelona | 1:1 (1:0) | ||
| R | Espanyol Barcelona | - | Rayo Vallecano | 0:1 (0:0) | ||
| H: 25.10.2006 20:45 | R: 08.11.2006 20:45 | Sieger: Rayo Vallecano | ||||
| H | Real Valladolid | - | Gimnàstic de Tarragona | 1:0 (0:0) | ||
| R | Gimnàstic de Tarragona | - | Real Valladolid | 1:3 (1:0) | ||
| H: 25.10.2006 20:45 | R: 08.11.2006 20:30 | Sieger: Real Valladolid | ||||
| H | Xerez CD | - | Getafe CF | 0:2 (0:0) | ||
| R | Getafe CF | - | Xerez CD | 1:2 (0:2) | ||
| H: 25.10.2006 21:00 | R: 08.11.2006 19:00 | Sieger: Getafe CF | ||||
| H | Málaga CF | - | Real Sociedad | 4:1 (1:1) | ||
| R | Real Sociedad | - | Málaga CF | 2:1 (1:0) | ||
| H: 25.10.2006 21:00 | R: 08.11.2006 20:00 | Sieger: Málaga CF | ||||
| H | Hércules CF | - | Real Zaragoza | 1:1 (1:0) | ||
| R | Real Zaragoza | - | Hércules CF | 2:0 (0:0) | ||
| H: 25.10.2006 21:00 | R: 08.11.2006 21:00 | Sieger: Real Zaragoza | ||||
| H | Recreativo Huelva | - | Real Betis | 0:0 (0:0) | ||
| R | Real Betis | - | Recreativo Huelva | 2:0 (1:0) | ||
| H: 25.10.2006 21:30 | R: 08.11.2006 22:00 | Sieger: Real Betis | ||||
| H | CD Castellón | - | Villarreal CF | 0:2 (0:2) | ||
| R | Villarreal CF | - | CD Castellón | 2:0 (1:0) | ||
| H: 25.10.2006 21:30 | R: 08.11.2006 20:00 | Sieger: Villarreal CF | ||||
| H | CF Badalona | - | FC Barcelona | 1:2 (0:0) | ||
| R | FC Barcelona | - | CF Badalona | 4:0 (2:0) | ||
| H: 25.10.2006 22:00 | R: 08.11.2006 22:00 | Sieger: FC Barcelona | ||||
| H | Athletic Club | - | RCD Mallorca | 1:1 (1:0) | ||
| R | RCD Mallorca | - | Athletic Club | 2:1 (1:0, 1:1) n.V. | ||
| H: 25.10.2006 22:00 | R: 08.11.2006 22:00 | Sieger: RCD Mallorca | ||||
