The Parisian club has now won the season-opening cup on 14 different occasions.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the match between the French league champions and the Coupe de France winners after Ousmane Dembele opened the net in the opening stages.
Yet, Marseille fired twice in the closing moments to take a surprise advantage. Initially, the English forward scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial leveler in the final moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 shootout win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past thirteen years.
