The Parisian club has now claimed the prestigious cup on 14 separate times.
Paris Saint-Germain required a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a fourth straight Trophee des Champions title.
The European champions seemed to be coasting towards a comfortable triumph in the match featuring the French league champions and the Coupe de France holders after the French winger opened the scoring in the opening stages.
However, Marseille struck two times late to take a surprise lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital equaliser in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a 4-1 penalty victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the past 13 seasons.
