The Parisian club has now claimed the season-opening cup on 14 different times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward triumph in the match featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring early on.
However, the southern French side struck two times late to seize a shock advantage. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker snatched a crucial leveler in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a convincing shootout victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the past thirteen years.
