PSG has now secured the prestigious cup on 14 separate occasions.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the Coupe de France winners after the French winger opened the net in the opening stages.
However, the southern French side struck two times late to take a surprise lead. Initially, the English forward converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker snatched a crucial equaliser in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted successfully for PSG to complete a convincing penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the last thirteen years.