The Parisian club has now secured the prestigious trophy on 14 separate occasions.
The Parisian giants needed a dramatic leveler 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 European champions appeared to be coasting towards a comfortable win in the showdown between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele opened the net early on.
Yet, Marseille struck two times in the closing moments to seize a shock advantage. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial equaliser in the final seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive attempts from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 shootout victory.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the past thirteen years.