The Parisian club has now won the prestigious trophy on 14 separate occasions.
Paris Saint-Germain required a dramatic leveler followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be coasting towards a straightforward win in the match featuring the French league winners and the Coupe de France holders after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck two times late to take a shock lead. Initially, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial equaliser in the final moments to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing shootout victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
