PSG has now secured the prestigious cup on fourteen separate occasions.
The Parisian giants needed a dramatic leveler followed by a successful penalty shootout to get past Marseille in the Gulf and secure 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 winners and the French Cup holders after Ousmane Dembele found the net early on.
Yet, Marseille fired two times in the closing moments to seize a surprise advantage. First, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored successfully for PSG to seal a convincing shootout win.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this competition for the 12th time in the last thirteen years.
