PSG has now secured the prestigious cup on 14 separate occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a comfortable triumph in the showdown between the Ligue 1 champions and the French Cup holders after the French winger found the scoring in the opening stages.
However, the southern French side struck two times late to take 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 remarkable twist of events, Goncalo Ramos grabbed a crucial leveler in the final moments to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for PSG to seal a 4-1 penalty victory.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
