PSG has now won the season-opening trophy on 14 separate occasions.
The Parisian giants 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 sailing towards a comfortable triumph in the match featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the net early on.
However, Marseille fired two times late to seize a shock lead. Initially, Mason Greenwood scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital equaliser in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 shootout win.
The record winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the last thirteen seasons.
