The Parisian club has now secured the season-opening cup on fourteen separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a comfortable triumph in the showdown between the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille struck twice in the closing moments to take a shock advantage. First, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos snatched a vital equaliser in the final moments to send the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive attempts from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted with composure for Paris Saint-Germain to complete a convincing penalty win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last 13 seasons.
