The Parisian club has now won the prestigious cup on 14 separate occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful penalty shootout to get past Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward win in the match between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
However, Marseille fired two times late to seize a shock lead. Initially, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital leveler in the final moments to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored successfully for Paris Saint-Germain to complete a 4-1 penalty victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past thirteen seasons.
