PSG has now claimed the season-opening cup on fourteen different times.
The Parisian giants required a stoppage-time equaliser followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable win in the showdown between the Ligue 1 winners and the Coupe de France winners after the French winger found the scoring early on.
However, Marseille struck twice in the closing moments to seize a surprise advantage. Initially, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital equaliser in the dying moments to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving crucial kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted with composure for Paris Saint-Germain to seal a convincing shootout victory.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past thirteen years.
