PSG has now secured the prestigious trophy on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions seemed to be sailing towards a straightforward triumph in the showdown between the French league champions and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
However, the southern French side struck two times late to seize a shock lead. First, the English forward converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital leveler in the dying moments to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a 4-1 shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the past 13 seasons.
