The Parisian club has now claimed the season-opening cup on 14 different occasions.
The Parisian giants required a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the net early on.
However, Marseille struck twice in the closing moments to seize a shock lead. First, the English forward scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker snatched a crucial leveler in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted successfully for PSG to seal a 4-1 shootout win.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the past thirteen years.
