The Parisian club has now won the prestigious trophy on 14 different times.
The Parisian giants required a stoppage-time leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a straightforward triumph in the showdown featuring the French league winners and the Coupe de France winners after Ousmane Dembele found the net early on.
However, Marseille fired twice late to seize a surprise lead. First, 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 turn of events, Goncalo Ramos snatched a vital equaliser in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive kicks from Matt O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to complete a 4-1 penalty win.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the last 13 seasons.
