The Parisian club has now claimed the prestigious cup on 14 separate occasions.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a straightforward triumph in the showdown between the French league winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side struck twice in the closing moments to seize a surprise lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a vital leveler in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive kicks from Matt O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for PSG to seal a convincing shootout victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last thirteen years.
