The Parisian club has now secured the prestigious trophy on fourteen different times.
The Parisian giants needed a stoppage-time equaliser followed by a successful penalty shootout to get past their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the scoring early on.
However, Marseille fired two times late to seize a surprise lead. First, Mason Greenwood scored from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos snatched a vital leveler in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the last thirteen years.
