The Parisian club has now won the prestigious cup on fourteen separate occasions.
The Parisian giants required a dramatic leveler followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable win in the showdown featuring the Ligue 1 champions and the French Cup winners after the French winger opened the net early on.
However, the southern French side struck twice in the closing moments to take a shock lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital equaliser in the final moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to seal a convincing shootout win.
The record winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last thirteen seasons.