PSG has now won the prestigious trophy on 14 different occasions.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and capture a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a comfortable win in the match between the French league champions and the French Cup holders after the French winger found the net in the opening stages.
However, the southern French side fired two times in the closing moments to take a surprise advantage. Initially, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a crucial leveler in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last thirteen years.