All kick-off times in GMT.
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- Sun, Feb 24, 2013
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| FT | Rayo Vallecano | 1 - 2 | Real Valladolid |
| FT | Celta Vigo | 2 - 1 | Granada |
| FT | Atletico Madrid | 1 - 0 | Espanyol |
| FT | Real Betis | 3 - 0 | Malaga |
| FT | Real Madrid Castilla | 2 - 1 | Guadalajara |
| FT | Almeria | 4 - 1 | Ponferradina |
| FT | Girona | 2 - 0 | Cordoba |
| FT | Elche | 3 - 1 | Huesca |
| FT | Villarreal | 1 - 1 | Las Palmas |
| FT | Xerez | 0 - 1 | CD Sabadell |
| FT | Sampdoria | 2 - 0 | Chievo Verona |
| FT | Atalanta | 2 - 3 | AS Roma |
| FT | Cagliari | 4 - 3 | Torino |
| FT | Juventus | 3 - 0 | Siena |
| FT | Parma | 1 - 2 | Catania |
| FT | Internazionale | 1 - 1 | AC Milan |
| FT | Energie Cottbus | 1 - 1 | SSV Jahn Regensburg |
| FT | SV Sandhausen | 1 - 3 | SC Paderborn 07 |
| FT | TSV Eintracht Braunschweig | 1 - 2 | TSV 1860 Munich |
| FT | Feyenoord Rotterdam | 2 - 1 | PSV Eindhoven |
| FT | Ajax Amsterdam | 1 - 1 | ADO Den Haag |
| FT | FC Utrecht | 4 - 0 | Roda JC Kerkrade |
| FT | AZ Alkmaar | 0 - 1 | NAC Breda |
| FT | Kayserispor | 1 - 0 | Genclerbirligi |
| FT | Fenerbahce | 3 - 1 | Kasimpasa |
| FT | Karabukspor | 0 - 2 | Akhisar Belediye |
| FT | Asteras Tripoli | 1 - 0 | Levadiakos |
| FT | Atromitos | 0 - 0 | Giannina |
| FT | Panionios | 2 - 0 | Panthrakikos |
| FT | Platanias | 2 - 1 | AEK Athens |
| FT | Olympiakos | 2 - 1 | Aris Salonika |
| FT | Atletico Rafaela | 1 - 2 | Godoy Cruz de Mendoza |
| FT | Independiente | 2 - 0 | Racing Club |
| FT | Belgrano de Córdoba | 2 - 1 | Colón de Santa Fe |
| FT | River Plate | 3 - 2 | Tigre |
| FT | Universidad Católica | 4 - 0 | Unión La Calera |
| FT | Antofagasta | 1 - 2 | Everton CD |
| FT | Universidad de Chile | 6 - 1 | Arica |
| FT | Bella Vista | 0 - 1 | Racing (U) |
| FT | Juventud | 0 - 4 | River Plate |
| FT | Liverpool | 0 - 1 | Danubio F.C. |
| FT | Progreso | 2 - 1 | Cerro |
| FT | Nacional | 0 - 1 | Defensor Sporting |
| FT | Alianza Petrolera | 0 - 1 | Independiente Medellín |
| FT | Cúcuta Deportivo | 0 - 0 | Deportivo Cali |
| FT | Deportivo Pasto | 1 - 0 | Atlético Junior |
| FT | Independiente Santa Fe | 2 - 0 | Deportes Quindío |
| FT | Melgar FBC | 0 - 2 | Alianza Lima |
| FT | Unión Comercio | 2 - 0 | San Martin |
| FT | UTC | 3 - 1 | Inti Gas Deportes |
| FT | Nacional | 1 - 0 | Libertad |
| FT | Rubio Ñú | 1 - 2 | Deportivo Capiatá |
| FT | Sol de América | 0 - 0 | Sp. Carapeguá |
| FT | Cerro Porteño | 4 - 2 | Cerro Porteño de Franco |
| FT | Manta F.C. | 3 - 1 | Club Deportivo Cuenca |
| FT | Deportivo Quevedo | 0 - 0 | LDU Quito |
| FT | Atlético Vigía | 3 - 0 | Portuguesa |
| FT | Yaracuyanos | 0 - 1 | Dep. Petare |
| FT | Atlético Venezuela | 0 - 2 | Zamora |
| FT | Zulia | 1 - 2 | Anzoátegui |
| FT | Llaneros | 0 - 0 | Aragua |
| FT | Monagas SC | 1 - 0 | Estudiantes de Mérida |
| FT | A.C. Mineros | 1 - 1 | Real Espor |
| FT | Caracas F.C. | 3 - 0 | CD Lara |
| FT | Deportivo Táchira | 1 - 1 | Trujillanos |
| FT | Real Potosí | 4 - 0 | Blooming |
| FT | Aurora | 0 - 6 | Wilstermann |
| FT | La Paz | 1 - 2 | The Strongest |
| FT | Oriente Petrolero | 1 - 1 | Nacional Potosí |
| FT | San Carlos | 1 - 1 | Perez Zeledon |
| FT | Belen | 2 - 0 | Puntarenas |
| FT | Club Sport Uruguay | 1 - 1 | Cartagines |