The Parisian club has now claimed the prestigious trophy on fourteen separate times.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the match featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille struck two times in the closing moments to seize a surprise advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a crucial leveler in the final moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for PSG to seal a 4-1 penalty victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the 12th time in the past thirteen years.