The Parisian club has now won the season-opening cup on 14 different 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 fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward win in the match featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring early on.
Yet, Marseille struck two times late to take a shock lead. First, the English forward converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital equaliser in the dying moments to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the past thirteen seasons.
