PSG has now claimed the season-opening cup on fourteen different times.
The Parisian giants required a dramatic leveler followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and capture a record-extending fourth consecutive Trophee des Champions title.
The European champions appeared to be coasting towards a comfortable win in the showdown between the French league champions and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
Yet, the southern French side fired two times late to seize a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital leveler in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a convincing shootout win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the last thirteen years.