PSG has now won the prestigious cup on 14 separate times.
The Parisian giants required a dramatic equaliser followed by a successful penalty shootout to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable triumph in the match between the French league winners and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side fired twice late to take a shock lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital equaliser in the final seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to complete a 4-1 penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the twelfth time in the last thirteen seasons.
