The Parisian club has now claimed the prestigious cup on 14 different times.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable triumph in the showdown between the Ligue 1 winners and the French Cup winners after the French winger opened the net early on.
However, the southern French side struck twice in the closing moments to seize a surprise lead. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial equaliser in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for PSG to complete a convincing shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the 12th time in the last thirteen seasons.
