The Parisian club has now won the prestigious trophy on 14 separate occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders seemed to be coasting towards a comfortable win in the match featuring the French league champions and the French Cup holders after the French winger found the scoring early on.
Yet, Marseille fired two times in the closing moments to seize a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of events, the Portuguese striker grabbed a vital leveler in the dying seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to seal a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the twelfth time in the last 13 years.