The Parisian club has now claimed the season-opening cup on fourteen different occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a straightforward win in the match between the Ligue 1 champions and the French Cup holders after the French winger opened the scoring early on.
Yet, the southern French side fired two times in the closing moments to take a shock lead. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the final seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past thirteen years.
