PSG has now claimed the prestigious trophy on fourteen different times.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward triumph in the match featuring the French league winners and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
However, Marseille struck twice in the closing moments to take a shock advantage. Initially, the English forward scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital leveler in the dying moments to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for PSG to complete a convincing penalty victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the past 13 years.
