PSG has now claimed 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 record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the showdown between the French league champions and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
However, Marseille fired two times late to take a shock lead. First, the English forward converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial equaliser in the final moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a 4-1 shootout victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the last thirteen seasons.
