PSG has now won the prestigious cup on 14 separate occasions.
Paris Saint-Germain required a dramatic leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a comfortable triumph in the match featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille fired twice late to take a shock advantage. First, the English forward scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial leveler in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing shootout win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this competition for the twelfth time in the last thirteen years.
