PSG has now won the prestigious cup on 14 separate times.
The Parisian giants needed a dramatic leveler followed by a successful penalty shootout to overcome Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward triumph in the match featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
Yet, Marseille struck twice in the closing moments to seize a surprise advantage. First, the English forward scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a vital equaliser in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a 4-1 penalty victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this competition for the twelfth time in the past 13 seasons.
