The Parisian club has now won the prestigious cup on 14 different occasions.
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 secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the Coupe de France winners after the French winger found the scoring early on.
However, Marseille fired two times in the closing moments to take a shock advantage. First, the English forward converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital leveler in the final moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to seal a convincing shootout victory.
The record champions PSG, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last thirteen seasons.
