Real-P.S.G. and Barcelona-Chelsea in the Champions League

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NYON, Switzerland — Real Madrid versus Paris St.-Germain. Cristiano Ronaldo versus Neymar. Historic achievement versus burning ambition.

Real Madrid, the two-time defending Champions League winner, was drawn on Monday to play P.S.G., one of the tournament’s standout teams, in the last 16. This was made possible because Real, a 12-time champion, finished second in its group while P.S.G. won its group.

“They are really very strong in every department of the field,” said Real’s director, Emilio Butragueño. “But I have to underline, we are the holders, and our players, they always rise to the occasion.”

P.S.G. bought the rights to Neymar from Barcelona for a record fee of 222 million euros ($262 million) in the off-season. Neymar scored in five straight wins as the team finished ahead of Bayern Munich in its group.

Ronaldo scored in all six of Real Madrid’s matches.

Barcelona, which leads the Spanish league, was drawn to face Chelsea in a meeting of recent champions. Chelsea, from the Premier League, is one of the few opponents Lionel Messi has failed to score against.

With eight former winners in the lineup, another clash of European champions pits Liverpool against Porto. The other matchups are Basel versus Manchester City, Sevilla versus Manchester United, Juventus versus Tottenham, Bayern Munich versus Besiktas, and Shakhtar Donetsk versus Roma.

The first legs will be played from Feb. 13 to 21, with the return matches from March 6 to 14. The final will be played at the Olympic Stadium in Kiev, Ukraine, on May 26.

Real Madrid and Paris St.-Germain met in the group stage two seasons ago, when P.S.G.’s leader was Zlatan Ibrahimovic. They drew, 0-0, in Paris, and Real won, 1-0, at home.

“Since then they have strengthened — they have signed very, very good players,” said Butragueño, whose club lost out to P.S.G. in its pursuit of the French forward Kylian Mbappé.

Barcelona and Chelsea will renew a rivalry that has included intense semifinals in 2009 and 2012. Each took a turn to advance at the other team’s stadium and go on to win the title.