PSG has now won the prestigious trophy on 14 different occasions.
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 coasting towards a comfortable triumph in the match between the Ligue 1 champions and the Coupe de France holders after the French winger found the scoring in the opening stages.
Yet, Marseille struck twice late to take a surprise lead. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial equaliser in the final moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the last thirteen years.
