The Parisian club has now claimed the season-opening cup on 14 separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the match featuring the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the net early on.
Yet, Marseille struck twice in the closing moments to take a surprise advantage. First, 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 twist of fortune, the Portuguese striker snatched a crucial leveler in the final seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 penalty win.
The record winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the last 13 seasons.
