The Parisian club has now claimed the prestigious trophy on 14 separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be coasting towards a straightforward triumph in the match between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the scoring early on.
However, the southern French side fired twice in the closing moments to seize a shock advantage. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker grabbed a crucial equaliser in the final moments to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for PSG to complete a 4-1 penalty victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the last 13 seasons.
