PSG has now claimed the prestigious cup on 14 different occasions.
The Parisian giants needed a dramatic leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward win in the showdown between the Ligue 1 champions and the French Cup winners after the French winger opened the net in the opening stages.
Yet, Marseille fired twice late to seize a shock 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 turn of events, the Portuguese striker snatched a vital equaliser in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to complete a 4-1 penalty win.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the past thirteen years.
