The play-off round was split into two separate sections: one for champions and one for non-champions. The losing teams in both sections entered the 2013–14 UEFA Europa League group stage.

The draw for the play-off round was held on 9 August 2013.[30] The first legs were played on 20 and 21 August, and the second legs were played on 27 and 28 August 2013.

On 14 August 2013, Metalist Kharkiv were disqualified from the 2013–14 UEFA club competitions because of previous match-fixing.[18] UEFA decided to replace Metalist Kharkiv in the Champions League play-off round with PAOK, who were eliminated by Metalist Kharkiv in the third qualifying round.[19]

Red Bull Salzburg lodged a protest after being defeated by Fenerbahçe in the third qualifying round, but it was rejected by UEFA and the Court of Arbitration for Sport.[31]2013-14 UEFA Champions League qualifying phase and play-off round