PSG has now claimed the season-opening trophy on 14 separate occasions.
Paris Saint-Germain needed a dramatic leveler followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown featuring the French league champions and the Coupe de France winners after Ousmane Dembele opened the net early on.
However, the southern French side struck twice late to seize a surprise advantage. Initially, the English forward scored from the spot-kick, before the defender inadvertently turned 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 force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a convincing penalty win.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past thirteen seasons.
