The Parisian club has now secured the prestigious cup on fourteen different occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward win in the showdown between the French league champions and the French Cup holders after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side struck twice late to seize a surprise advantage. First, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial equaliser in the final moments to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood 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 convincing penalty win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past 13 years.
