The Parisian club has now won the season-opening cup on fourteen separate times.
The Parisian giants needed a dramatic leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown featuring the French league winners and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
However, the southern French side fired twice late to seize a shock lead. Initially, the English forward scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos snatched a crucial leveler in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to seal a 4-1 shootout win.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past 13 seasons.
