PSG has now claimed the season-opening cup on 14 separate occasions.
The Parisian giants needed a stoppage-time 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 coasting towards a straightforward triumph in the match between the French league champions and the French Cup holders after the French winger found the net in the opening stages.
However, Marseille struck two times in the closing moments to take a surprise lead. Initially, the English forward converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital equaliser in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to complete a convincing penalty win.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last 13 years.
