PSG has now claimed the season-opening cup on fourteen different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to get past Marseille in Kuwait and secure a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a straightforward win in the showdown between the French league winners and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck two times late to seize a shock advantage. First, the English forward scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial equaliser in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the last thirteen seasons.