The Parisian club has now claimed the season-opening trophy on 14 separate occasions.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a straightforward win in the showdown between the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, Marseille fired twice late to seize a surprise lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial equaliser in the dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for PSG to complete a 4-1 penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the past thirteen years.
