The Parisian club has now won the prestigious cup on fourteen different times.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to get past Marseille in Kuwait and capture 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 French Cup holders after Ousmane Dembele opened the net in the opening stages.
However, Marseille struck two times in the closing moments to take a shock advantage. First, the English forward converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos grabbed a vital equaliser in the dying moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
