All kick-off times in GMT.
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- Sun, Jan 27, 2013
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| FT | Real Madrid | 4 - 0 | Getafe |
| FT | Rayo Vallecano | 3 - 0 | Real Betis |
| FT | Barcelona | 5 - 1 | Osasuna |
| FT | Athletic Bilbao | 3 - 0 | Atletico Madrid |
| FT | Mallorca | 2 - 3 | Malaga |
| FT | AD Alcorcon | 1 - 0 | Ponferradina |
| FT | Barcelona B | 3 - 1 | Real Madrid Castilla |
| FT | Mirandes | 2 - 1 | Recreativo Huelva |
| FT | Numancia | 1 - 2 | Huesca |
| FT | Xerez | 0 - 2 | Almeria |
| FT | Bologna | 3 - 3 | AS Roma |
| FT | Atalanta | 0 - 1 | AC Milan |
| FT | Cagliari | 1 - 1 | Palermo |
| FT | Catania | 2 - 1 | Fiorentina |
| FT | Parma | 1 - 2 | Napoli |
| FT | Sampdoria | 6 - 0 | US Pescara |
| FT | Udinese | 1 - 0 | Siena |
| FT | Internazionale | 2 - 2 | Torino |
| FT | Vitesse Arnhem | 3 - 2 | Ajax Amsterdam |
| FT | FC Utrecht | 3 - 1 | Willem II Tilburg |
| FT | Feyenoord Rotterdam | 0 - 0 | Twente Enschede |
| FT | NEC Nijmegen | 2 - 1 | FC Groningen |
| FT | Maritimo | 1 - 1 | Rio Ave |
| FT | Moreirense | 0 - 5 | Paços de Ferreira |
| FT | Vitoria Setubal | 0 - 2 | CD Nacional de Madeira |
| FT | Sporting Lisbon | 1 - 1 | Guimaraes |
| FT | Estoril | 3 - 3 | Olhanense |
| FT | Kayserispor | 2 - 0 | Antalyaspor |
| FT | Elazigspor | 3 - 1 | Trabzonspor |
| FT | Mersin Idmanyurdu | 3 - 0 | Sivasspor |
| FT | Galatasaray | 2 - 1 | Besiktas |
| FT | Giannina | 2 - 0 | Veria |
| FT | Panthrakikos | 0 - 1 | Olympiakos |
| FT | PAOK Salonika | 0 - 1 | FC Xanthi |
| FT | Platanias | 0 - 3 | Asteras Tripoli |
| FT | Atromitos | 1 - 2 | Panathinaikos |
| FT | Defensa y Justicia | 2 - 1 | Deportivo Merlo |
| FT | Patronato | 2 - 0 | Nueva Chicago |
| FT | Olimpo de Bahía Blanca | 4 - 1 | Aldosivi |
| FT | Atlético Vigía | 0 - 1 | Atlético Venezuela |
| FT | Real Espor | 1 - 0 | Dep. Petare |
| FT | Trujillanos | 2 - 1 | Estudiantes de Mérida |
| FT | A.C. Mineros | 2 - 2 | Llaneros |
| FT | Caracas F.C. | 1 - 1 | Aragua |
| FT | CD Lara | 0 - 3 | Zamora |
| FT | Monagas SC | 2 - 1 | Zulia |