The Parisian club has now claimed the season-opening cup on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be sailing towards a comfortable win in the showdown between the Ligue 1 champions and the French Cup holders after the French winger opened the net in the opening stages.
However, the southern French side struck two times in the closing moments to take a shock advantage. Initially, the English forward scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial equaliser in the final seconds to force the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing penalty victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last thirteen seasons.
