The Parisian club has now won the season-opening cup on 14 separate times.
Paris Saint-Germain required a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and capture a record-extending fourth consecutive Trophee des Champions victory.
The European champions appeared to be sailing towards a comfortable triumph in the showdown between the French league winners and the Coupe de France winners after Ousmane Dembele found the scoring early on.
However, the southern French side struck twice late to seize a shock lead. 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 remarkable twist of events, the Portuguese striker grabbed a crucial leveler in the dying moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the last thirteen seasons.
