The Parisian club has now won the season-opening cup on 14 different times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward win in the showdown between the French league winners and the Coupe de France holders after the French winger found the scoring in the opening stages.
Yet, the southern French side fired two times late to seize a surprise advantage. Initially, the English forward scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial leveler in the dying moments to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to seal a 4-1 penalty win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last 13 seasons.
