The Parisian club has now secured the season-opening cup on fourteen different occasions.
The Parisian giants required a dramatic equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a comfortable win in the showdown featuring the Ligue 1 champions and the French Cup winners after the French winger found the scoring early on.
Yet, Marseille struck twice in the closing moments to seize a shock lead. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital leveler in the dying moments to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to seal a convincing penalty win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past 13 seasons.
