The Parisian club has now won the prestigious cup on 14 different times.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable triumph in the showdown between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille struck twice late to take a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender 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 dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted successfully for Paris Saint-Germain to complete a convincing penalty victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the 12th time in the last thirteen years.
