PSG has now won the prestigious trophy on fourteen separate occasions.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive Trophee des Champions victory.
The European champions seemed to be sailing towards a straightforward win in the match between the French league champions and the French Cup holders after the French winger opened the net early on.
Yet, the southern French side fired two times in the closing moments to seize a surprise lead. First, the English forward scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital leveler in the dying moments to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to seal a 4-1 penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this competition for the twelfth time in the past thirteen years.