The Parisian club has now secured the season-opening cup on 14 different occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable triumph in the match between the French league champions and the French Cup winners after Ousmane Dembele opened the scoring early on.
However, Marseille fired two times in the closing moments to take a shock advantage. First, the English forward converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital equaliser in the dying seconds to send the match 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, Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to complete a convincing shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this trophy for the 12th time in the past 13 seasons.
