The Parisian club has now won the season-opening cup on fourteen separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a comfortable win in the match between the French league champions and the Coupe de France holders after Ousmane Dembele opened the net early on.
Yet, Marseille struck twice in the closing moments to take a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital leveler in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to seal a convincing shootout win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the last thirteen years.
