PSG has now won the prestigious trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown between the Ligue 1 champions and the French Cup winners after the French winger found the net in the opening stages.
Yet, the southern French side struck two times in the closing moments to take a surprise lead. Initially, the English forward scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital equaliser in the final moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored successfully for PSG to complete a 4-1 penalty win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past thirteen seasons.
