The Parisian club has now won the prestigious cup on 14 different times.
The Parisian giants required a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and secure a record-extending fourth consecutive Trophee des Champions victory.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the Coupe de France winners after the French winger found the scoring in the opening stages.
Yet, Marseille struck two times in the closing moments to take a shock lead. Initially, the English forward scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker grabbed a vital leveler in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to seal a 4-1 penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the past 13 years.