The first leg will take place at the Stadio Olimpico in Rome on Wednesday 17 February, with the second leg being played at the Santiago Bernabeu in Madrid on 8 March.
Madrid topped Group A with 16 points, having won five and drawn one of their group matches with a scoring record of 19 goals for and three against. PSG finished as runners-up.
Roma, meanwhile, qualified as the second-placed team in Group E behind Barcelona, earning a place in the knock-out rounds for the first time in five years.
Incidentally, it was Real Madrid that Roma beat over two legs in the last 16 of the 2007-08 edition of the Champions League to seal their most recent qualification to the quarter-final stage.
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