PSG has now won the season-opening trophy on 14 separate times.
The Parisian giants required a stoppage-time leveler followed by a perfect penalty shootout to overcome Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable win in the match between the Ligue 1 champions and the Coupe de France holders after the French winger opened the scoring early on.
However, the southern French side fired twice late to seize a shock 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 fortune, Goncalo Ramos grabbed a vital leveler in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to complete a convincing penalty victory.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the last thirteen seasons.
