PSG has now secured the season-opening trophy on fourteen different occasions.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and secure a fourth straight Trophee des Champions title.
The Champions League holders appeared to be coasting towards a straightforward win in the showdown featuring the French league champions and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, the southern French side fired twice in the closing moments to seize a surprise lead. Initially, the English forward 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 fortune, the Portuguese striker snatched a crucial equaliser in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past thirteen years.