PSG has now won the prestigious trophy on 14 different occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match featuring the Ligue 1 winners and the Coupe de France winners after the French winger opened the scoring in the opening stages.
However, the southern French side struck two times late to take a surprise lead. First, the English forward converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker grabbed a crucial equaliser in the final seconds to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past 13 seasons.
