PSG has now claimed the season-opening trophy on fourteen different occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
However, Marseille fired two times in the closing moments to take a shock advantage. Initially, the English forward scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos grabbed a crucial leveler in the final moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all converted successfully for Paris Saint-Germain to seal a convincing penalty victory.
The record winners PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the last 13 years.
