The Parisian club has now secured the prestigious trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable triumph in the match featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring early on.
However, Marseille fired twice in the closing moments to take a shock advantage. First, the English forward converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a vital equaliser in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last thirteen years.
