The Parisian club has now secured the prestigious trophy on fourteen separate times.
The Parisian giants required a dramatic equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a straightforward triumph in the showdown featuring the French league winners and the Coupe de France winners after Ousmane Dembele opened the net in the opening stages.
However, Marseille struck two times in the closing moments to seize a shock advantage. Initially, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos grabbed a vital leveler in the final seconds to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 shootout win.
The record winners PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
