The Parisian club has now secured the prestigious cup on 14 different times.
Paris Saint-Germain required a dramatic equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be sailing towards a straightforward triumph in the showdown between the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck two times in the closing moments to take a surprise lead. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital leveler in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing shootout victory.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the past thirteen seasons.
