PSG has now won the season-opening cup on 14 different occasions.
Paris Saint-Germain needed a stoppage-time equaliser 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 appeared to be sailing towards a straightforward win in the showdown featuring the French league champions and the Coupe de France winners after the French winger found the net early on.
Yet, Marseille fired two times in the closing moments to seize a shock advantage. Initially, the English forward scored from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a crucial leveler in the dying moments to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last 13 seasons.
