PSG has now won the season-opening trophy on 14 different occasions.
Paris Saint-Germain required a dramatic leveler followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the net early on.
Yet, the southern French side struck two times late to take a surprise lead. First, Mason Greenwood converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial leveler in the dying moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing penalty victory.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the last 13 seasons.
