PSG has now claimed the season-opening trophy on 14 separate occasions.
The Parisian giants required a dramatic leveler followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be coasting towards a comfortable win in the showdown featuring the French league champions and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille struck two times late to seize a surprise lead. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital leveler in the final seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
The record winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the last thirteen years.
