PSG has now claimed the season-opening cup on fourteen different occasions.
The Parisian giants required a stoppage-time equaliser followed by a successful 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 comfortable win in the match featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the net early on.
Yet, the southern French side fired two times late to take a shock advantage. First, the English forward scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial equaliser in the dying seconds to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the last 13 years.
