Real Madrid will play Manchester City in the Champions League round of 16, and holders Liverpool will face Atletico Madrid.
The draw in Nyon, Switzerland, on Monday brought up some fascinating ties, with the heavyweight clashes between England's and Madrid's top clubs arguably the pick of the bunch.
Jurgen Klopp's men, who beat Tottenham 2-0 in the final last season to lift the trophy for a sixth time, will return to the Wanda Metropolitano to face Atleti, while Pep Guardiola's City face a tough test against 13-time winners Real Madrid.
City, who will be at home in the second leg, have yet to beat the Spanish side, with two draws and two defeats in their previous four meetings.
However, Guardiola has a much more encouraging record with nine wins, four draws and four defeats in 17 meetings as coach of Barcelona and then Bayern Munich.
"It's a difficult one," said Manchester City's director of football, Txiki Begiristain. "Real Madrid are the best. We want to be the best, so we have to try and beat them. It's always a pleasure to play against Real Madrid. We know them very well. They know our manager."
Chelsea will meet Bayern Munich in a repeat of the 2012 final, when Blues boss Frank Lampard lifted the trophy as captain. Borussia Dortmund will face Paris Saint-Germain, with PSG manager Thomas Tuchel returning to face his former club.
Hasan Salihamidzic, Bayern's sporting director, said: "Chelsea have done very well with their young players. It's an attractive tie. We accept the challenge, of course, and want to go through."
Bayern goalkeeper Manuel Neuer added: "We're excited to go to London; we have some good memories there. Chelsea are dangerous team. We need to take them seriously and with focus. Of course, we want to go through to the next round."
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CEO Hans-Joachim Watzke called Dortmund's clash with PSG "50-50," while the Ligue 1 side's sporting director, Leonardo, told RMC: "It is always difficult. If it had been another team, my speech may well have been the same as it is now. In the latter stages of the Champions League, you can come up against anybody -- teams that are always difficult. Borussia are a side that plays. True, though, the scenario is a good one. We have the coach who knows the atmosphere and the team well. It will be special for him."
Lyon face Juventus, while Jose Mourinho's Tottenham were drawn against Bundesliga leaders RB Leipzig. Elsewhere, debutants Atalanta will meet Valencia and Napoli will play Barcelona.
"It's a tough draw. There will be a great atmosphere at their stadium for the first leg. You never know how the two teams will be when the games come around," Barca coach Ernesto Valverde said.
"There will be a fierce atmosphere at a stadium where the fans are right on top of you. We're used to playing in these atmospheres and it will be nice to see everything that's generated around this game in Naples."
Atalanta's place in the knockout round is a surprise in itself, with the Serie A side going through after failing to win any of their opening four matches in the group stage.
For the first time in Champions League history, all 16 teams in the knockout stages are from the top five ranked leagues in Europe: England, Spain, Italy, Germany and France.
The first legs will be played on Feb. 18 and 19 and Feb. 25 and 26, with the return legs on March 10 and 11 and March 17 and 18.
The final is on May 30 in the Turkish city of Istanbul.
Full Draw
Borussia Dortmund vs. Paris Saint-Germain
Real Madrid vs. Manchester City
Atalanta vs. Valencia
Atletico Madrid vs. Liverpool
Chelsea vs. Bayern Munich
Lyon vs. Juventus
Tottenham vs. RB Leipzig
Napoli vs. Barcelona
ROUND OF 16 DRAW CALENDAR IN FULL
Tuesday, Feb. 18, 2020
Borussia Dortmund vs. PSG
Atletico Madrid vs. Liverpool
Wednesday, Feb. 19
Atalanta vs. Valencia
Tottenham vs. RB Leipzig
Tuesday, Feb. 25
Napoli vs. Barcelona
Chelsea vs. Bayern Munich
Wednesday, Feb. 26
Real Madrid vs. Manchester City
Lyon vs. Juventus
Tuesday, March 10
Valencia vs. Atalanta
RB Leipzig vs. Tottenham
Wednesday, March 11
PSG vs. Borussia Dortmund
Liverpool vs. Atletico Madrid
Tuesday, March 17
Manchester City vs. Real Madrid
Juventus vs. Lyon
Wednesday, March 18
Barcelona vs. Napoli
Bayern Munich vs. Chelsea
Information from Reuters was used in this report.