The Parisian club has now secured the season-opening trophy on 14 different times.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful penalty shootout to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a straightforward triumph in the showdown between the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the scoring early on.
Yet, Marseille struck two times in the closing moments to take a surprise lead. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a vital equaliser in the final seconds to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving decisive attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to seal a 4-1 penalty win.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the twelfth time in the past thirteen years.