The Parisian club has now secured the prestigious trophy on 14 separate occasions.
Paris Saint-Germain needed a dramatic leveler followed by a successful penalty shootout to get past their arch-rivals in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a straightforward triumph in the match between the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
However, the southern French side struck two times late to take a surprise lead. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker snatched a crucial equaliser in the dying moments to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted successfully for PSG to seal a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past 13 seasons.
