PSG has now won the season-opening cup on fourteen different times.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight Trophee des Champions victory.
The European champions appeared to be sailing towards a straightforward win in the showdown between the French league champions and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
Yet, Marseille fired twice in the closing moments to seize a surprise lead. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital equaliser in the dying moments to force the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this competition for the twelfth time in the past 13 seasons.