PSG has now secured the prestigious trophy on 14 separate times.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown between the French league champions and the Coupe de France winners after Ousmane Dembele found the scoring early on.
Yet, the southern French side struck two times in the closing moments to take a surprise advantage. First, Mason Greenwood 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, Goncalo Ramos snatched a crucial equaliser in the final seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past thirteen seasons.