PSG has now claimed the prestigious trophy on 14 separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown between the French league champions and the Coupe de France holders after Ousmane Dembele opened the net early on.
Yet, Marseille struck two times late to seize a surprise lead. First, the English forward scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of events, the Portuguese striker grabbed a vital leveler in the dying seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored with composure for Paris Saint-Germain to seal 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 completing a domestic double, have now lifted this trophy for the twelfth time in the last thirteen years.