The Parisian club has now won the season-opening cup on 14 separate occasions.
Paris Saint-Germain needed a dramatic leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match featuring the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side struck two times in the closing moments to take a shock advantage. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker grabbed a crucial leveler in the final moments to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing shootout victory.
Now 14-time winners PSG, 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.
