The Parisian club has now claimed the prestigious cup on 14 different times.
The Parisian giants required a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a comfortable triumph in the showdown between the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille fired twice in the closing moments to seize a shock lead. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately 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 seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for PSG to complete a convincing shootout win.
The record winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the past 13 years.
