The Parisian club has now won the season-opening trophy on 14 separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown between the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the scoring early on.
Yet, the southern French side struck twice late to take a shock lead. First, the English forward converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a vital equaliser in the final moments to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored successfully for PSG to seal a convincing penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the 12th time in the last 13 seasons.
