The Parisian club has now claimed the prestigious cup on fourteen separate times.
The Parisian giants 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 victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the match featuring the French league winners and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, Marseille struck twice in the closing moments to seize a shock advantage. First, Mason Greenwood scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a vital leveler in the final moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to complete a 4-1 penalty win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the 12th time in the last thirteen years.