PSG has now claimed the prestigious trophy on 14 different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be sailing towards a comfortable win in the match featuring the French league champions and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille fired two times in the closing moments to take a shock lead. First, the English forward converted from the spot-kick, before the defender unfortunately directed 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 final seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for PSG to seal a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the last 13 years.
