All kick-off times in BST.
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- Sat, Sep 15, 2012
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| FT | St Johnstone | 2 - 1 | Celtic |
| FT | Dundee | 1 - 2 | Motherwell |
| FT | Hibernian | 2 - 1 | Kilmarnock |
| FT | Inverness Caledonian Thistle | 1 - 1 | Aberdeen |
| FT | St Mirren | 2 - 0 | Heart of Midlothian |
| FT | Cowdenbeath | 3 - 4 | Greenock Morton |
| FT | Dumbarton | 0 - 2 | Dunfermline Athletic |
| FT | Hamilton Academical | 1 - 1 | Falkirk |
| FT | Livingston | 1 - 2 | Partick Thistle |
| FT | Raith Rovers | 2 - 0 | Airdrie United |
| FT | Albion Rovers | 2 - 1 | Stranraer |
| FT | Alloa Athletic | 0 - 2 | Stenhousemuir |
| FT | Arbroath | 2 - 0 | East Fife |
| FT | Ayr United | 2 - 4 | Queen of the South |
| FT | Forfar Athletic | 1 - 0 | Brechin City |
| FT | Annan Athletic | 0 - 0 | Rangers |
| FT | East Stirlingshire | 3 - 1 | Stirling Albion |
| FT | Elgin City | 2 - 0 | Peterhead |
| FT | Montrose | 3 - 1 | Berwick Rangers |
| FT | Queen's Park | 1 - 0 | Clyde |
| FT | Troyes | 1 - 1 | Lille |
| FT | Evian Thonon Gaillard | 3 - 0 | Bastia |
| FT | Nice | 4 - 2 | Brest |
| FT | St Etienne | 0 - 1 | Sochaux |
| FT | Valenciennes | 0 - 0 | Bordeaux |
| FT | Ajax Amsterdam | 2 - 0 | RKC Waalwijk |
| FT | Heerenveen | 1 - 3 | ADO Den Haag |
| FT | VVV Venlo | 2 - 2 | NEC Nijmegen |
| FT | Willem II Tilburg | 2 - 6 | Twente Enschede |
| FT | Feyenoord Rotterdam | 2 - 0 | PEC Zwolle |
| FT | Kasimpasa | 3 - 0 | Gaziantepspor |
| FT | Antalyaspor | 0 - 4 | Galatasaray |
| FT | Bursaspor | 4 - 1 | Karabukspor |
| FT | Lierse SK | 1 - 1 | Anderlecht |
| FT | Cercle Brugge KSV | 0 - 1 | KSC Lokeren |
| FT | KAA Gent | 0 - 2 | KV Mechelen |
| FT | OH Leuven | 0 - 1 | Zulte-Waregem |
| FT | Racing Genk | 1 - 1 | Waasland-Beveren |
| FT | RAEC Bergen Mons | 2 - 3 | Royal Charleroi SC |
| FT | Wolfsberger AC | 6 - 0 | FC Magna Wr. Neustadt |
| FT | Rapid Vienna | 0 - 0 | FC Trenkwalder Admira |
| FT | SK Sturm Graz | 3 - 0 | FC Wacker Tirol |
| FT | SV Salzburg | 1 - 1 | SV Josko Ried |
| FT | Ballinamallard Utd | 2 - 0 | Portadown |
| FT | Ballymena | 1 - 1 | Dungannon Swifts |
| FT | Crusaders | 2 - 0 | Donegal Celtic |
| FT | Glentoran | 0 - 0 | Coleraine |
| FT | Linfield | 1 - 2 | Cliftonville |
| FT | Lisburn Distillery | 0 - 1 | Glenavon |
| FT | Tigre | 2 - 2 | Colón de Santa Fe |
| FT | All Boys | 0 - 1 | Argentinos Juniors |
| FT | Godoy Cruz de Mendoza | 1 - 0 | San Martín de San Juan |
| FT | Racing Club | 0 - 1 | Estudiantes La Plata |
| FT | Rangers de Talca | 2 - 2 | Universidad de Chile |
| FT | Cobresal | 2 - 1 | Santiago Wanderers |
| FT | Universidad de Concepción | 0 - 1 | Municipal Iquique |
| FT | O'Higgins | 1 - 0 | Cobreloa |
| FT | Unión San Felipe | 3 - 0 | La Serena |
| FT | Itagüí | 1 - 0 | Millonarios |
| FT | La Equidad | 2 - 0 | Deportivo Pasto |
| FT | Once Caldas | 0 - 1 | Independiente Medellín |
| FT | Atlético Huila | 1 - 0 | Envigado |
| Group A | |||
|---|---|---|---|
| FT | Inti Gas Deportes | 1 - 1 | Sporting Cristal |
| Group B | |||
| FT | César Vallejo | 2 - 0 | Unión Comercio |