The knockout phase involved the 16 teams which qualified as winners and runners-up of each of the eight groups in the group stage. Each tie in the knockout phase, apart from the final, was played over two legs, with each team playing one leg at home. The team that scored more goals on aggregate over the two legs advanced to the next round. If the aggregate score was level, the away goals rule was applied, i.e., the team that scored more goals away from home over the two legs advanced. If away goals were also equal, then thirty minutes of extra time was played. The away goals rule was again applied after extra time, i.e., if there were goals scored during extra time and the aggregate score was still level, the visiting team advanced by virtue of more away goals scored. If no goals were scored during extra time, the tie was decided by penalty shoot-out. In the final, which was played as a single match, if scores were level at the end of normal time, extra time was played, followed by penalty shoot-out if scores remained tied. The mechanism of the draws for each round was as follows:
In the draw for the round of 16, the eight group winners were seeded, and the eight group runners-up were unseeded. The seeded teams were drawn against the unseeded teams, with the seeded teams hosting the second leg. Teams from the same group or the same association could not be drawn against each other.
In the draws for the quarter-finals onwards, there were no seedings, and teams from the same group or the same association could be drawn against each other.
Qualified teams
Bracket
Round of 16
The draw was held on 16 December 2013. The first legs were played on 18, 19, 25 and 26 February, and the second legs were played on 11, 12, 18 and 19 March 2014.
First leg
---- ---- ---- ---- ---- ---- ----
Second leg
Atlético Madrid won 5–1 on aggregate. ---- Bayern Munich won 3–1 on aggregate. ---- Barcelona won 4–1 on aggregate. ---- Paris Saint-Germain won 6–1 on aggregate. ---- Chelsea won 3–1 on aggregate. ---- Real Madrid won 9–2 on aggregate. ---- Manchester United won 3–2 on aggregate. ---- Borussia Dortmund won 5–4 on aggregate.
Quarter-finals
The draw was held on 21 March 2014. The first legs were played on 1 and 2 April, and the second legs were played on 8 and 9 April 2014.
First leg
---- ---- ----
Second leg
Real Madrid won 3–2 on aggregate. ---- 3–3 on aggregate. Chelsea won on away goals. ---- Atlético Madrid won 2–1 on aggregate. ---- Bayern Munich won 4–2 on aggregate.
Semi-finals
The draw was held on 11 April 2014. The first legs were played on 22 and 23 April, and the second legs were played on 29 and 30 April 2014.
First leg
----
Second leg
Real Madrid won 5–0 on aggregate. ---- Atlético Madrid won 3–1 on aggregate.
