PSG has now claimed the prestigious cup on fourteen separate times.
The Parisian giants required a stoppage-time equaliser followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a comfortable triumph in the showdown featuring the French league champions and the French Cup winners after Ousmane Dembele opened the scoring early on.
Yet, Marseille struck twice late to seize a surprise lead. First, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital equaliser in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping crucial attempts from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted successfully for PSG to complete a convincing shootout victory.
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 competition for the twelfth time in the last thirteen seasons.
