PSG has now won the prestigious cup on 14 different times.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the showdown between the Ligue 1 champions and the French Cup winners after the French winger opened the net early on.
Yet, the southern French side struck two times in the closing moments to seize a surprise advantage. Initially, the English forward converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a vital equaliser in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to complete a convincing penalty win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this competition for the 12th time in the past 13 seasons.
