Unai Emery's men set up a repeat of the Coupe de la Ligue final – which they won last week – by beating third-tier outfit Avranches 4-0 to reach the last four on Wednesday.
Hatem Ben Arfa scored twice, with Lucas Moura and Javier Pastore also on target in an away win that ensured PSG will play Ligue 1 leaders Monaco, who are three points ahead of them with eight games left to play.
Despite trailing in the league, it was PSG who got the better of Leonardo Jardim's men in Saturday's Coupe de la Ligue showpiece, Emery's men winning 4-1 at Parc Olympique Lyonnais courtesy of goals from Julian Draxler, Angel Di Maria and a double from Edinson Cavani.
Monaco beat Lille 2-1 in their Coupe de France quarter-final on Tuesday to enter the draw for the last four.
The big two being drawn against each other means Angers host Guingamp in the other semi-final.
Coupe de France semi-final draw:
Angers v Guingamp
PSG v Monaco