The Parisian club has now won the season-opening cup on 14 separate times.
Paris Saint-Germain required a dramatic leveler followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable win in the showdown featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the net early on.
Yet, the southern French side struck twice in the closing moments to take 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 remarkable twist of fortune, Goncalo Ramos snatched a vital leveler in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this trophy for the 12th time in the last thirteen seasons.
