The Parisian club has now won the season-opening cup on fourteen different times.
The Parisian giants needed a dramatic equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward win in the match between the French league winners and the Coupe de France winners after the French winger opened the net early on.
However, Marseille fired twice late to take a shock advantage. First, the English forward converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos grabbed a vital leveler in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to complete a convincing shootout victory.
The record winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last 13 seasons.
