The Parisian club has now won the prestigious cup on 14 separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown featuring the Ligue 1 champions and the French Cup winners after the French winger opened the net in the opening stages.
Yet, the southern French side struck two times late to seize a shock lead. First, the English forward scored from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos snatched a crucial leveler in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to seal a convincing shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past thirteen years.
