The Parisian club has now won the prestigious trophy on fourteen separate times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and secure a fourth straight Trophee des Champions title.
The Champions League holders appeared to be sailing towards a straightforward win in the showdown featuring the French league champions and the Coupe de France winners after the French winger opened the scoring early on.
However, Marseille struck twice in the closing moments to take a surprise lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial equaliser in the final seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 shootout win.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last 13 seasons.
