The Parisian club has now won the prestigious cup on fourteen separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful penalty shootout to overcome Marseille in the Gulf and capture a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a straightforward triumph in the match between the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the scoring early on.
However, Marseille struck two times late to seize a shock advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently 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 dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for PSG to complete a convincing shootout win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the last thirteen seasons.
