The Parisian club has now won the season-opening cup on 14 different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a comfortable triumph in the showdown between the Ligue 1 winners and the French Cup winners after the French winger opened the scoring early on.
Yet, the southern French side struck twice late to take a surprise lead. Initially, Mason Greenwood 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 events, Goncalo Ramos grabbed a crucial equaliser in the dying seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG 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 domestic double, have now lifted this competition for the 12th time in the last 13 seasons.
