The Parisian club has now won the season-opening trophy on 14 separate times.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful penalty shootout to get past their arch-rivals 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 win in the showdown featuring the Ligue 1 champions and the French Cup holders after the French winger found the scoring in the opening stages.
Yet, Marseille struck two times in the closing moments to take a surprise lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a crucial equaliser in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive attempts from Matt O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this competition for the 12th time in the last 13 seasons.
