The Parisian club has now won the prestigious cup on 14 separate occasions.
Paris Saint-Germain required a dramatic leveler followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward win in the match between the French league champions and the Coupe de France winners after the French winger opened the net early on.
However, the southern French side struck two times late to seize a surprise advantage. First, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital equaliser in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 penalty victory.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the past 13 years.
