The Parisian club has now won the season-opening trophy on fourteen separate times.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the match between the French league winners and the Coupe de France holders after Ousmane Dembele found the scoring early on.
However, Marseille struck twice late to take a shock lead. First, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a crucial leveler in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored successfully for Paris Saint-Germain to complete a convincing penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the 12th time in the past thirteen years.
