The Parisian club has now won the prestigious cup on fourteen separate times.
The Parisian giants needed a dramatic equaliser followed by a perfect penalty shootout to overcome Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a comfortable win in the showdown featuring the Ligue 1 winners and the Coupe de France holders after the French winger found the scoring in the opening stages.
Yet, the southern French side struck twice in the closing moments to take a shock lead. First, the English forward converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial equaliser in the dying moments to force the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to complete a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the past 13 years.
