CD Castellón 0-4 Villarreal CF
| 08.11.2006 | Villarreal CF | 2-0 | CD Castellón | |
| 25.10.2006 | CD Castellón | 0-2 | Villarreal CF | |
*Deportivo Alavés 1-0 Celta de Vigo
| 09.11.2006 | Celta de Vigo | 0-1 | Deportivo Alavés | |
| 24.10.2006 | Deportivo Alavés | 0-0 | Celta de Vigo | |
Écija Balompié 2-6 Real Madrid *
| 09.11.2006 | Real Madrid | 5-1 | Écija Balompié | |
| 25.10.2006 | Écija Balompié | 1-1 | Real Madrid | |
CF Badalona 1-6 FC Barcelona
| 08.11.2006 | FC Barcelona | 4-0 | CF Badalona | |
| 25.10.2006 | CF Badalona | 1-2 | FC Barcelona | |
Atlético Madrid 1-1 Levante UD
| 13.12.2006 | Levante UD | 0-1/p.2-3 | Atlético Madrid | |
| 24.10.2006 | Atlético Madrid | 0-1 | Levante UD | |
Peña Sport FC 0-4 CA Osasuna
| 08.11.2006 | CA Osasuna | 4-0 | Peña Sport FC | |
| 25.10.2006 | Peña Sport FC | 0-0 | CA Osasuna | |
Racing Portuense 1-4 Valencia CF
| 08.11.2006 | Valencia CF | 2-0 | Racing Portuense | |
| 25.10.2006 | Racing Portuense | 1-2 | Valencia CF | |
Deportivo La Coruña 1-1 Racing Santander
| 08.11.2006 | Racing Santander | 1-0/p.1-3 | Deportivo La Coruña | |
| 25.10.2006 | Deportivo La Coruña | 1-0 | Racing Santander | |
Rayo Vallecano 2-1 RCD Espanyol
| 08.11.2006 | RCD Espanyol | 0-1 | Rayo Vallecano | |
| 25.10.2006 | Rayo Vallecano | 1-1 | RCD Espanyol | |
Recreativo Huelva 0-2 Real Betis
| 08.11.2006 | Real Betis | 2-0 | Recreativo Huelva | |
| 25.10.2006 | Recreativo Huelva | 0-0 | Real Betis | |
Athletic Bilbao 2-3 Real Mallorca
| 08.11.2006 | Real Mallorca | 2-1 AET | Athletic Bilbao | |
| 25.10.2006 | Athletic Bilbao | 1-1 | Real Mallorca | |
Málaga CF 5-3 Real Sociedad
| 08.11.2006 | Real Sociedad | 2-1 | Málaga CF | |
| 25.10.2006 | Málaga CF | 4-1 | Real Sociedad | |
Real Valladolid 4-1 Gimnàstic Tarragona
| 08.11.2006 | Gimnàstic Tarragona | 1-3 | Real Valladolid | |
| 25.10.2006 | Real Valladolid | 1-0 | Gimnàstic Tarragona | |
Hércules CF 1-3 Real Zaragoza
| 08.11.2006 | Real Zaragoza | 2-0 | Hércules CF | |
| 25.10.2006 | Hércules CF | 1-1 | Real Zaragoza | |
Gimn. Segoviana 0-4 Sevilla FC
| 08.11.2006 | Sevilla FC | 3-0 | Gimn. Segoviana | |
| 25.10.2006 | Gimn. Segoviana | 0-1 | Sevilla FC | |