Mauricio Pochettino side went behind to Lionel Messi's 27th-minute penalty.
But the equaliser came when Mbappe danced past Clement Lenglet and smashed into the net from 10 yards before he added his second five minutes later to turn the game around.
While On-loan Everton striker Moise Kean headed in unchallenged at the far post to put the Ligue 1 champions in control of the tie.
Mbappe curled in the goal of the night with his third to complete his hat-trick.
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