| 1. Round | 21/07/2013 | 1. FC Union Berlin | - | VfL Bochum | 1:2 |  |
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| 2. Round | 26/07/2013 | Arminia Bielefeld | - | 1. FC Union Berlin | 1:1 | |
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| 12. Round | 27/10/2013 | 1. FC Union Berlin | - | Erzgebirge Aue | 1:0 | ||||
| 17. Round | 07/12/2013 | TSV 1860 München | - | 1. FC Union Berlin | 2:1 | |
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| 18. Round | 14/12/2013 | VfL Bochum | - | 1. FC Union Berlin | 0:4 | ||||
| 19. Round | 21/12/2013 | 1. FC Union Berlin | - | Arminia Bielefeld | 4:2 |  |
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| 20. Round | 08/02/2014 | 1. FC Union Berlin | - | Dynamo Dresden | 0:0 | ||||
| 21. Round | 14/02/2014 | Fortuna Düsseldorf | - | 1. FC Union Berlin | 1:1 | ||||
| 22. Round | 21/02/2014 | 1. FC Union Berlin | - | FSV Frankfurt | 2:0 | ||||
| 23. Round | 03/03/2014 | FC St. Pauli | - | 1. FC Union Berlin | 2:1 | ||||
| 24. Round | 08/03/2014 | 1. FC Union Berlin | - | FC Ingolstadt 04 | 1:1 | ||||
| 25. Round | 16/03/2014 | SpVgg Greuther Fürth | - | 1. FC Union Berlin | 1:1 | |
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| 26. Round | 21/03/2014 | 1. FC Union Berlin | - | SC Paderborn 07 | 1:1 | ||||
| 27. Round | 25/03/2014 | SV Sandhausen | - | 1. FC Union Berlin | 2:1 |
Switzerland