PSG has now claimed the season-opening cup on 14 separate times.
Paris Saint-Germain required a dramatic leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward win in the showdown featuring the French league champions and the Coupe de France holders after Ousmane Dembele found the scoring in the opening stages.
However, Marseille struck twice late to seize a shock lead. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital leveler in the dying moments to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing shootout win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the last thirteen years.
