PSG has now claimed the season-opening trophy on 14 different occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions victory.
The European champions seemed to be sailing towards a comfortable triumph in the showdown featuring the French league champions and the Coupe de France holders after the French winger found the scoring early on.
However, the southern French side fired two times in the closing moments to take a surprise lead. Initially, the English forward scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker snatched a crucial leveler in the final seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted with composure for PSG to seal a 4-1 penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the past thirteen years.