The Parisian club has now secured the prestigious cup on 14 different times.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the net in the opening stages.
Yet, Marseille fired twice in the closing moments to seize a surprise lead. Initially, Mason Greenwood scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a vital leveler in the dying moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the 12th time in the last 13 seasons.
