PSG has now won the season-opening cup on fourteen separate occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the match featuring the French league winners and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
Yet, Marseille fired two times late to take a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a vital leveler in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the last 13 seasons.