The Parisian club has now claimed the prestigious trophy on fourteen different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a comfortable win in the showdown between the French league winners and the French Cup holders after the French winger opened the net early on.
However, the southern French side struck twice in the closing moments to seize a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a crucial leveler in the dying moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing shootout win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the last 13 seasons.
