The Parisian club has now won the prestigious trophy on 14 different occasions.
Paris Saint-Germain needed a dramatic leveler followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and secure a record-extending fourth consecutive Trophee des Champions title.
The European champions seemed to be coasting towards a straightforward triumph in the match featuring the Ligue 1 winners and the Coupe de France holders after the French winger opened the net in the opening stages.
Yet, the southern French side fired two times late to seize a shock lead. First, Mason Greenwood converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos grabbed a crucial equaliser in the dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the last 13 years.
