The Parisian club has now secured the prestigious cup on 14 separate occasions.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a straightforward win in the match between the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the scoring early on.
Yet, Marseille fired twice late to seize a surprise lead. Initially, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker grabbed a crucial leveler in the final moments to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past thirteen seasons.
