The Parisian club has now secured the season-opening trophy on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the match between the Ligue 1 winners and the Coupe de France winners after the French winger opened the scoring early on.
However, the southern French side struck two times late to take a surprise advantage. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital equaliser in the final moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to seal a convincing shootout victory.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last thirteen seasons.
