PSG has now secured the prestigious cup on fourteen separate times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable win in the showdown featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the net early on.
However, the southern French side struck twice in the closing moments to seize a shock advantage. First, the English forward converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos snatched a crucial equaliser in the final seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing penalty win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this competition for the 12th time in the past thirteen seasons.
