The Parisian club has now won the prestigious trophy on fourteen separate times.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be sailing towards a straightforward win in the showdown featuring the Ligue 1 champions and the French Cup holders after the French winger found the net in the opening stages.
Yet, Marseille struck twice late to take a shock advantage. First, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker snatched a vital leveler in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing shootout win.
The record winners PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past thirteen years.
