PSG has now won the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown featuring the Ligue 1 champions and the French Cup holders after the French winger opened the net in the opening stages.
Yet, the southern French side struck twice in the closing moments to take a surprise lead. Initially, the English forward converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a vital equaliser in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to seal a convincing shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past 13 years.
