The Parisian club has now claimed the season-opening cup on fourteen separate occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward win in the match featuring the French league champions and the French Cup winners after Ousmane Dembele found the net early on.
However, Marseille struck twice in the closing moments to take a shock lead. Initially, the English forward scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos grabbed a vital leveler in the final moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to complete a 4-1 penalty victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
