The Parisian club has now won the prestigious trophy on fourteen separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive Trophee des Champions victory.
The European champions seemed to be sailing towards a straightforward triumph in the showdown featuring the French league champions and the Coupe de France holders after Ousmane Dembele opened the net early on.
Yet, the southern French side struck two times late to take a surprise advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial equaliser in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a convincing penalty win.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this trophy for the 12th time in the last thirteen years.
