The Parisian club has now claimed the season-opening cup on 14 separate times.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a comfortable triumph in the match featuring the French league champions and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side fired two times in the closing moments to seize a shock lead. Initially, the English forward scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker grabbed a crucial equaliser in the dying moments to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the past thirteen years.
