PSG has now secured the prestigious cup on fourteen different times.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be sailing towards a comfortable win in the showdown featuring the French league champions and the Coupe de France holders after Ousmane Dembele found the net early on.
However, the southern French side struck twice late to seize a surprise lead. First, Mason Greenwood scored 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, Goncalo Ramos grabbed a vital leveler in the dying moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing shootout win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the last thirteen years.
