PSG has now claimed the season-opening cup on 14 separate occasions.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a straightforward win in the match between the French league winners and the Coupe de France winners after Ousmane Dembele opened the net early on.
Yet, the southern French side fired two times late to seize a surprise advantage. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a vital leveler in the dying moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing shootout victory.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.
