The Parisian club has now won the season-opening trophy on 14 separate occasions.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown between the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the scoring early on.
Yet, Marseille fired two times late to seize a shock lead. First, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital equaliser in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to seal a 4-1 penalty win.
Now 14-time champions Paris Saint-Germain, who faced 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 years.
