Manchester City, who will be at home in the second leg, have yet to beat Real Madrid with two draws and two defeats in their previous four meetings.
Thirteen-times winners Real Madrid were drawn against English champions Manchester City while title-holders Liverpool must face Diego Simeone’s Atletico Madrid in the Champions League round of 16 following Monday’s draw.
Real Madrid ended up in pot two after finishing second in their group behind Paris St Germain and City were the unlucky team to be paired with them when their name was pulled out at UEFA headquarters.
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, their manager Pep 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.”
Liverpool and Atletico Madrid’s previous meetings have produced one win for each team and two draws with both teams scoring four goals.
Only Europe’s biggest five leagues — England, France, Germany, Italy and Spain — were represented in the draw and 11 of the 16 teams also reached the knockout stages last season.
Both England and Spain managed to get all four of their teams into knockout stages. Elsewhere, Serie A champions Juventus will face French side Olympique Lyonnais and PSG will play Borussia Dortmund.
Barcelona were pitted against an unpredictable Napoli, the first time the two sides have ever met.
Napoli fired coach Carlo Ancelotti immediately after beating Genk to make sure of their place in the last 16 and replaced him with Gennaro Gattuso, who has never coached in the Champions League before.
“A great team, a great challenge, two fascinating races. We will face them without fear,” he said.
Jose Mourinho’s Tottenham Hotspur side, who reached the final last season, will play RB Leipzig, who are in the knockout stages for the first time, while Chelsea were drawn against Bayern Munich.
Despite their erratic domestic form, Bayern were the only team to complete the group stage with a 100% record.
Serie A side Atalanta, who reached the last 16 on their first participation in the Champions League despite losing their first three group matches, were drawn against Valencia.
Draw for the Champions League round of 16 on Monday (first named-team plays first leg at home):
Real Madrid v Manchester City
Atalanta v Valencia
Atletico Madrid v Liverpool
Chelsea v Bayern Munich
Olympique Lyonnais v Juventus
Tottenham Hotspur v RB Leipzig
Napoli v Barcelona
First legs to be played on February 18, 19, 25, 26. Second legs to be played in March.
Europa League: Manchester United draw Club Brugge
Manchester United will continue their Europa League campaign against Belgian side Club Brugge after Monday's draw for the last 32 of the competition at UEFA headquarters.
Three-time European champions United, arguably the biggest name in the draw, qualified as group winners while Brugge drop in from the Champions League after finishing behind Paris St Germain and Real Madrid.
Ajax Amsterdam's consolation for exiting the Champions League at the group phase is a two-legged tie with Spanish side Getafe, while Inter Milan face Bulgarians Ludogorets.
"We've not had a lot of luck in the draw," Getafe's sporting director Angel Martin Gonzales said. "They're a big side but that helps us grow, too."
Two other clubs who failed to progress to the Champions League knockout rounds face off with Benfica up against Shakhtar Donetsk. AS Roma play Gent while former European champions Porto face Bayer Leverkusen, one of three German clubs in the draw.
Sevilla, the most successful club in Europa League history with five titles, play Romanian outfit CFR Cluj.
Eintracht Frankfurt face Champions League drop-outs Salzburg while VfL Wolfsburg take on Malmo.
United are one of three English clubs in the last 32 with Arsenal handed a testing tie against Greek club Olympiakos Piraeus. Wolverhampton Wanderers face Espanyol in what will be their first clash with a Spanish club since losing 9-2 on aggregate to Barcelona in the 1959-60 European Cup quarter-finals.
"It's a big challenge for us to play against Arsenal, last year's UEFA Europa League finalists," Olympiakos coach Pedro Martins said. "They may not have started well in the Premier League this season, but they have great players, are dangerous and deserve our respect."
Scotland's former European champions Celtic are up against Copenhagen while Rangers face Portuguese club Braga. Sporting take on Turkish side Istanbul Basaksehir.
