The Parisian club has now secured the season-opening cup on 14 different times.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to get past Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the net early on.
However, the southern French side struck two times in the closing moments to seize a shock advantage. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of events, the Portuguese striker grabbed a crucial leveler in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for PSG to seal a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the past thirteen seasons.