The Parisian club has now secured the prestigious cup on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown featuring the French league winners and the French Cup holders after Ousmane Dembele opened the scoring early on.
Yet, the southern French side struck two times in the closing moments to seize a surprise advantage. Initially, the English forward converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos grabbed a vital equaliser in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing shootout victory.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this competition for the 12th time in the last 13 years.
