PSG has now won the season-opening cup on 14 separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a comfortable win in the match between the French league champions and the French Cup holders after the French winger found the scoring in the opening stages.
Yet, Marseille struck twice late to take a shock lead. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial equaliser in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to complete a 4-1 shootout win.
The record winners Paris Saint-Germain, 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 twelfth time in the past 13 years.
