The Parisian club has now secured the prestigious cup on fourteen different occasions.
The Parisian giants needed a dramatic equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward win in the showdown featuring the Ligue 1 winners and the French Cup holders after the French winger opened the net early on.
However, Marseille fired twice late to take a surprise lead. Initially, the English forward scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital equaliser in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to seal a convincing shootout victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the past 13 years.
