PSG has now claimed the prestigious cup on fourteen different times.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and secure a fourth straight Trophee des Champions title.
The Champions League holders seemed to be coasting towards a straightforward win in the showdown between the Ligue 1 champions and the French Cup winners after Ousmane Dembele opened the net early on.
Yet, the southern French side struck twice late to seize a shock advantage. 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 turn of fortune, the Portuguese striker snatched a vital equaliser in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to complete a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the 12th time in the past thirteen seasons.
