PSG has now won the season-opening trophy on fourteen different occasions.
The Parisian giants required a dramatic equaliser followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the showdown between the French league winners and the Coupe de France winners after the French winger opened the scoring early on.
Yet, the southern French side fired two times in the closing moments to take a surprise lead. Initially, Mason Greenwood converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a vital equaliser in the dying seconds to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to complete a convincing shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
