PSG has now secured the prestigious trophy on 14 different occasions.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a straightforward triumph in the showdown between the Ligue 1 champions and the Coupe de France winners after the French winger opened the net early on.
Yet, the southern French side fired twice late to take a surprise lead. Initially, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial equaliser in the final seconds to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to seal a convincing penalty win.
The record winners PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the past 13 years.
