PSG has now claimed the prestigious trophy on fourteen different occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the net early on.
Yet, the southern French side struck two times in the closing moments to seize a surprise lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial equaliser in the final moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a 4-1 penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.
