PSG has now won the season-opening cup on fourteen different times.
The Parisian giants required a dramatic equaliser followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a comfortable win in the match between the Ligue 1 champions and the Coupe de France holders after the French winger found the net early on.
However, the southern French side fired twice in the closing moments to take a shock lead. First, the English forward scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital equaliser in the final seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to seal a 4-1 penalty win.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the past 13 seasons.
