The Parisian club has now claimed the season-opening cup on 14 different times.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful penalty shootout to get past their arch-rivals in Kuwait and secure a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger opened the net early on.
Yet, the southern French side struck twice late to seize a surprise lead. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital equaliser in the dying moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for PSG to complete a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the past thirteen seasons.
