PSG has now claimed the season-opening trophy on 14 different occasions.
The Parisian giants required a dramatic equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable win in the match between the French league winners and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
However, Marseille struck twice in the closing moments to seize a shock advantage. Initially, the English forward scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos snatched a crucial equaliser in the final seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to seal a 4-1 shootout win.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the last thirteen years.
