PSG has now secured the prestigious cup on fourteen different times.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the match between the French league winners and the French Cup holders after Ousmane Dembele found the net early on.
However, Marseille struck two times in the closing moments to take a shock lead. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital equaliser in the dying moments to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to complete a convincing penalty win.
The record winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the last thirteen seasons.
