The Parisian club has now claimed the prestigious cup on 14 different times.
Paris Saint-Germain required a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a straightforward win in the showdown featuring the French league winners and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck two times late to take a shock lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital equaliser in the dying moments to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past thirteen years.
