The Parisian club has now secured the season-opening cup on 14 different times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side struck twice in the closing moments to seize a shock lead. Initially, the English forward converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker grabbed a crucial leveler in the dying seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to complete a 4-1 shootout win.
The record champions PSG, who met 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 13 years.
