PSG has now claimed the season-opening trophy on fourteen separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions seemed to be sailing towards a straightforward win in the match between the Ligue 1 winners and the Coupe de France holders after the French winger found the scoring early on.
Yet, the southern French side fired twice in the closing moments to seize a surprise advantage. First, the English forward converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos grabbed a vital equaliser in the final moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this competition for the 12th time in the past thirteen seasons.
