| 2. Round | 17/08/2013 | SC Bastia | - | Valenciennes FC | 2:0 |  |
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| 3. Round | 24/08/2013 | Valenciennes FC | - | Olympique Marseille | 0:1 | ||||
| 4. Round | 31/08/2013 | FC Lorient | - | Valenciennes FC | 1:0 | ||||
| 5. Round | 14/09/2013 | Valenciennes FC | - | AS Saint-Étienne | 1:3 | ||||
| 6. Round | 22/09/2013 | OGC Nice | - | Valenciennes FC | 4:0 | ||||
| 7. Round | 25/09/2013 | Valenciennes FC | - | Paris Saint-Germain | 0:1 | ||||
| 8. Round | 28/09/2013 | FC Sochaux | - | Valenciennes FC | 2:0 | ||||
| 9. Round | 05/10/2013 | Valenciennes FC | - | Stade de Reims | 1:1 | ||||
| 12. Round | 02/11/2013 | AC Ajaccio | - | Valenciennes FC | 1:3 | ||||
| 13. Round | 09/11/2013 | Valenciennes FC | - | Montpellier HSC | 1:1 | ||||
| 15. Round | 30/11/2013 | Valenciennes FC | - | Lille OSC | 0:1 | ||||
| 19. Round | 20/12/2013 | AS Monaco | - | Valenciennes FC | 1:2 | ||||
| 29. Round | 15/03/2014 | Évian Thonon Gaillard | - | Valenciennes FC | 0:1 | ||||
| 31. Round | 29/03/2014 | Montpellier HSC | - | Valenciennes FC | 0:0 | ||||
| 32. Round | 06/04/2014 | Valenciennes FC | - | Olympique Lyonnais | 1:2 | |
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| 35. Round | 26/04/2014 | EA Guingamp | - | Valenciennes FC | 1:0 | ||||
| 38. Round | 17/05/2014 | Toulouse FC | - | Valenciennes FC | 3:1 |
France
Martinique