The Parisian club has now claimed the prestigious cup on fourteen different times.
Paris Saint-Germain required a dramatic leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown between the French league champions and the French Cup winners after the French winger found the scoring early on.
Yet, the southern French side struck two times in the closing moments to seize a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker snatched a vital leveler in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive kicks from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a convincing penalty victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the last 13 seasons.
