The Parisian club has now secured the season-opening cup on fourteen different occasions.
Paris Saint-Germain required a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown between the Ligue 1 champions and the Coupe de France winners after the French winger opened the scoring in the opening stages.
However, the southern French side struck twice in the closing moments to seize 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 remarkable turn of fortune, Goncalo Ramos snatched a crucial leveler in the final seconds to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 shootout win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last 13 seasons.