PSG has now won the prestigious trophy on 14 separate occasions.
The Parisian giants needed a dramatic equaliser followed by a successful penalty shootout to overcome Marseille in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable triumph in the match between the Ligue 1 champions and the French Cup holders after Ousmane Dembele found the scoring early on.
However, the southern French side struck twice in the closing moments to take a shock advantage. Initially, the English forward scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos snatched a vital leveler in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the past thirteen years.
