All kick-off times in GMT.
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- Sat, Feb 2, 2013
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| FT | Dundee United | 3 - 0 | Rangers |
| FT | Dunfermline Athletic | 0 - 2 | Hamilton Academical |
| FT | Falkirk | 4 - 1 | Forfar Athletic |
| FT | Kilmarnock | 2 - 0 | Inverness Caledonian Thistle |
| FT | St Mirren | 2 - 0 | St Johnstone |
| FT | Clyde | 1 - 1 | Elgin City |
| FT | Montrose | 2 - 2 | East Stirlingshire |
| FT | Peterhead | 1 - 1 | Berwick Rangers |
| FT | Queen's Park | 2 - 2 | Annan Athletic |
| FT | Osasuna | 1 - 0 | Celta Vigo |
| FT | Getafe | 3 - 1 | Deportivo La Coruña |
| FT | Espanyol | 3 - 2 | Levante |
| FT | Granada | 1 - 0 | Real Madrid |
| FT | CD Sabadell | 3 - 2 | Barcelona B |
| FT | Guadalajara | 0 - 0 | Villarreal |
| FT | Las Palmas | 0 - 0 | Elche |
| FT | Sporting Gijon | 1 - 2 | Racing Santander |
| FT | Hercules | 3 - 0 | AD Alcorcon |
| FT | Brescia | 0 - 0 | Spezia |
| FT | Cittadella | 2 - 2 | Crotone |
| FT | Grosseto | 1 - 1 | Padova |
| FT | Livorno | 2 - 0 | Pro Vercelli |
| FT | Novara | 0 - 1 | Cesena |
| FT | Sassuolo | 1 - 1 | Empoli |
| FT | Ternana | 0 - 0 | Bari |
| FT | Varese | 2 - 0 | Modena |
| FT | Vicenza | 1 - 2 | Juve Stabia |
| FT | Fortuna Düsseldorf | 3 - 1 | VfB Stuttgart |
| FT | Mainz | 0 - 3 | Bayern Munich |
| FT | Schalke 04 | 1 - 2 | SpVgg Greuther Furth |
| FT | TSG Hoffenheim | 2 - 1 | SC Freiburg |
| FT | VfL Wolfsburg | 1 - 1 | FC Augsburg |
| FT | Hamburg SV | 0 - 2 | Eintracht Frankfurt |
| FT | Lorient | 2 - 2 | Stade Rennes |
| FT | Bastia | 0 - 0 | Evian Thonon Gaillard |
| FT | Bordeaux | 2 - 0 | Valenciennes |
| FT | Brest | 0 - 2 | Nice |
| FT | Lille | 1 - 1 | Troyes |
| FT | Sochaux | 1 - 2 | St Etienne |
| FT | AZ Alkmaar | 0 - 1 | FC Groningen |
| FT | NAC Breda | 3 - 0 | PEC Zwolle |
| FT | Roda JC Kerkrade | 3 - 3 | SC Heracles Almelo |
| FT | PSV Eindhoven | 7 - 0 | ADO Den Haag |
| FT | KAA Gent | 2 - 1 | Germinal Beerschot |
| FT | Cercle Brugge KSV | 1 - 2 | Zulte-Waregem |
| FT | KV Kortrijk | 2 - 1 | KV Mechelen |
| FT | Lierse SK | 1 - 1 | KSC Lokeren |
| FT | OH Leuven | 1 - 0 | Royal Charleroi SC |
| FT | RAEC Bergen Mons | 3 - 0 | Waasland-Beveren |
| FT | Cliftonville | 4 - 0 | Lisburn Distillery |
| FT | Coleraine | 0 - 0 | Ballinamallard Utd |
| FT | Donegal Celtic | 0 - 3 | Crusaders |
| FT | Glenavon | 3 - 1 | Dungannon Swifts |
| FT | Linfield | 2 - 2 | Ballymena |
| FT | Portadown | 0 - 1 | Glentoran |
| FT | Airbus UK | 3 - 1 | Afan Lido |
| FT | Bala Town | 3 - 6 | Connah's Quay |
| FT | Bangor City | 2 - 2 | Port Talbot |
| FT | Carmarthen | 4 - 2 | Newtown |
| FT | T.N.S. | 3 - 0 | Aberystwyth |
| FT | Universidad Católica | 1 - 1 | Palestino |
| FT | O'Higgins | 2 - 0 | Santiago Wanderers |
| FT | Unión Española | 1 - 2 | Rangers de Talca |
| FT | Arica | 3 - 1 | Cobresal |
| FT | Alianza Petrolera | 0 - 3 | Independiente Santa Fe |
| FT | Deportivo Cali | 2 - 1 | Once Caldas |
| FT | Patriotas F.C. | 1 - 1 | Boyacá Chicó FC |
| FT | Atlético Nacional | 3 - 0 | Atlético Huila |