The Parisian club has now secured the prestigious trophy on fourteen separate occasions.
Paris Saint-Germain required a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a comfortable win in the showdown between the French league champions and the French Cup holders after the French winger found the net in the opening stages.
Yet, Marseille fired twice late to seize a shock lead. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a crucial leveler in the final seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive attempts from Matt O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the last thirteen seasons.
