PSG has now secured the prestigious cup on 14 separate occasions.
Paris Saint-Germain needed a dramatic leveler followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele found the net early on.
However, Marseille fired two times in the closing moments to seize a shock advantage. Initially, the English forward scored from the spot-kick, before the defender inadvertently turned 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 final moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial attempts from Matt O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for PSG to seal a 4-1 penalty win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past 13 years.