The Parisian club has now won the prestigious cup on 14 different occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a comfortable win in the showdown featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the net early on.
However, the southern French side fired twice in the closing moments to seize a surprise lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial leveler in the dying moments to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving decisive kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to seal a 4-1 shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last thirteen seasons.
