The Parisian club has now claimed the prestigious cup on fourteen different times.
Paris Saint-Germain required a dramatic leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a comfortable triumph in the showdown between the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
Yet, Marseille struck two times late to take a surprise advantage. Initially, the English forward converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker grabbed a crucial leveler in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the past 13 seasons.