PSG has now won the prestigious cup on 14 different occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the match featuring the French league winners and the French Cup holders after Ousmane Dembele found the scoring early on.
However, Marseille struck two times in the closing moments to seize a shock lead. 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 breathtaking turn of fortune, Goncalo Ramos snatched a vital equaliser in the final moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive kicks from Matt O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to complete a 4-1 penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past 13 seasons.
