PSG has now secured the season-opening cup on fourteen separate occasions.
Paris Saint-Germain 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 Champions League holders seemed to be coasting towards a straightforward win in the showdown featuring the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele opened the net in the opening stages.
However, the southern French side struck twice in the closing moments to take a shock advantage. First, the English forward scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a crucial leveler in the final moments to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to complete a convincing shootout win.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past 13 seasons.
