The Parisian club has now secured the season-opening cup on fourteen separate occasions.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a comfortable win in the match between the French league winners and the French Cup winners after Ousmane Dembele opened the scoring early on.
Yet, Marseille struck twice in the closing moments to take a surprise lead. Initially, the English forward scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital equaliser in the final moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to complete a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last 13 years.
