The Parisian club has now won the season-opening trophy on 14 separate occasions.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match featuring the French league winners and the French Cup winners after the French winger opened the net in the opening stages.
Yet, the southern French side struck twice in the closing moments to seize a shock lead. First, the English forward converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital leveler in the dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to complete a convincing penalty 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 won this competition for the 12th time in the last 13 seasons.
