The Parisian club has now won the prestigious trophy on fourteen different times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele opened the net early on.
However, the southern French side struck twice in the closing moments to seize a shock lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial leveler in the final moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive kicks from Matt O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to complete a convincing shootout victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the past 13 seasons.
