PSG has now won the season-opening trophy on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and capture a fourth straight Trophee des Champions title.
The Champions League holders appeared to be coasting towards a straightforward triumph in the match between the Ligue 1 champions and the French Cup holders after Ousmane Dembele found the scoring early on.
However, the southern French side struck two times late to take a surprise lead. Initially, the English forward converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial leveler in the final moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to complete a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the last 13 years.
