PSG has now claimed the prestigious cup on 14 different occasions.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the net early on.
Yet, Marseille fired two times in the closing moments to seize a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before the defender unfortunately 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 seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive kicks from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for PSG to complete a 4-1 shootout win.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this trophy for the 12th time in the last 13 seasons.
