The Parisian club has now won the prestigious trophy on fourteen separate times.
The Parisian giants required a dramatic leveler followed by a successful penalty shootout to get past Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a straightforward win in the showdown between the French league champions and the Coupe de France winners after Ousmane Dembele found the net early on.
Yet, Marseille fired two times late to take a surprise advantage. First, 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 twist of fortune, the Portuguese striker snatched a crucial leveler in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 shootout victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past thirteen seasons.