The Parisian club has now claimed the prestigious cup on 14 separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable win in the match between the French league winners and the Coupe de France winners after the French winger opened the scoring in the opening stages.
Yet, the southern French side struck two times late to seize a surprise lead. First, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial leveler in the dying seconds to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this trophy for the 12th time in the last thirteen years.
