PSG has now claimed the season-opening trophy on 14 different times.
The Parisian giants required a dramatic leveler followed by a perfect penalty shootout to overcome Marseille in Kuwait and capture a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the showdown between the French league winners and the French Cup winners after the French winger found the net early on.
Yet, Marseille fired twice late to seize a surprise advantage. Initially, the English forward scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital leveler in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored successfully for PSG to complete a convincing shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the last 13 seasons.
