PSG has now secured the prestigious cup on fourteen different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a comfortable win in the match between the Ligue 1 champions and the French Cup winners after the French winger found the scoring in the opening stages.
Yet, Marseille struck twice in the closing moments to seize a surprise lead. Initially, the English forward converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a crucial leveler in the dying moments to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all scored successfully for Paris Saint-Germain to seal a 4-1 shootout win.
The record winners PSG, who met 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 seasons.