The Parisian club has now claimed the prestigious cup on 14 separate times.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect penalty shootout to get past Marseille in Kuwait and secure a fourth straight Trophee des Champions victory.
The European champions appeared to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger found the net early on.
Yet, Marseille struck two times late to seize a shock advantage. First, the English forward scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital leveler in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to complete a 4-1 penalty win.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the past 13 years.
