The Parisian club has now won the prestigious cup on 14 separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a straightforward win in the match featuring the French league winners and the Coupe de France winners after the French winger opened the scoring in the opening stages.
However, Marseille struck two times late to take a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker snatched a vital equaliser in the final moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to complete a 4-1 shootout win.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the last thirteen seasons.
