The Parisian club has now won the season-opening cup on 14 different occasions.
The Parisian giants required a dramatic leveler followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward triumph in the match between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the scoring early on.
Yet, the southern French side struck two times late to seize a shock lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos grabbed a crucial equaliser in the final seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for PSG to complete a 4-1 penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the last thirteen seasons.
