The Parisian club has now claimed the season-opening cup on fourteen different occasions.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a straightforward triumph in the showdown between the French league winners and the Coupe de France winners after the French winger found the net in the opening stages.
Yet, Marseille fired two times in the closing moments to take a surprise advantage. First, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a crucial equaliser in the dying moments to force the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to complete a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last thirteen seasons.
