All kick-off times in GMT.
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- Sun, Jan 20, 2013
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| FT | Osasuna | 2 - 1 | Deportivo La Coruña |
| FT | Real Valladolid | 2 - 0 | Real Zaragoza |
| FT | Atletico Madrid | 2 - 0 | Levante |
| FT | Valencia | 0 - 5 | Real Madrid |
| FT | Cordoba | 5 - 0 | Murcia |
| FT | Hercules | 3 - 0 | Lugo |
| FT | Recreativo Huelva | 2 - 0 | Xerez |
| FT | Sporting Gijon | 1 - 1 | Numancia |
| FT | Almeria | 2 - 2 | Barcelona B |
| FT | Huesca | 0 - 1 | Mirandes |
| FT | Ponferradina | 1 - 1 | Elche |
| FT | Fiorentina | 1 - 1 | Napoli |
| FT | AC Milan | 2 - 1 | Bologna |
| FT | Chievo Verona | 1 - 1 | Parma |
| FT | Genoa | 0 - 2 | Catania |
| FT | Siena | 1 - 0 | Sampdoria |
| FT | US Pescara | 0 - 2 | Torino |
| FT | Atalanta | 1 - 1 | Cagliari |
| FT | AS Roma | 1 - 1 | Internazionale |
| FT | FC Groningen | 0 - 2 | FC Utrecht |
| FT | Ajax Amsterdam | 3 - 0 | Feyenoord Rotterdam |
| FT | Willem II Tilburg | 1 - 1 | ADO Den Haag |
| FT | Roda JC Kerkrade | 2 - 0 | NEC Nijmegen |
| FT | Atromitos | 1 - 0 | Platanias |
| FT | FC Xanthi | 0 - 0 | Kerkyra |
| FT | Olympiakos | 2 - 0 | Giannina |
| FT | Aris Salonika | 1 - 1 | AEK Athens |
| FT | Esportivo-RS | 0 - 2 | Gremio |
| FT | Santa Cruz | 1 - 2 | Cerámica |
| FT | São Luiz | 0 - 0 | Cruzeiro POA |
| FT | Ulbra | 0 - 0 | Caxias |
| FT | Veranópolis | 3 - 1 | Novo Hamburgo |
| FT | Atlético Venezuela | 2 - 0 | Zulia |
| FT | Trujillanos | 1 - 0 | Portuguesa |
| FT | Yaracuyanos | 2 - 2 | Monagas SC |
| FT | Estudiantes de Mérida | 0 - 0 | Real Espor |
| FT | Zamora | 1 - 1 | Caracas F.C. |
| FT | Aragua | 0 - 0 | Atlético Vigía |
| FT | Petrolero | 3 - 1 | Aurora |
| FT | Real Potosí | 3 - 1 | Oriente Petrolero |
| FT | The Strongest | 0 - 0 | San José |
| FT | Wilstermann | 3 - 2 | Nacional Potosí |
| FT | Blooming | 0 - 1 | Universitario de Sucre |
| FT | Cartagines | 2 - 0 | Carmelita |
| FT | Santos | 0 - 2 | Saprissa |
| FT | Club Sport Uruguay | 4 - 1 | San Carlos |
| FT | CD Motagua | 0 - 1 | C.D.Real Sociedad |
| FT | Vida | 0 - 2 | Olimpia |