The Parisian club has now secured the prestigious cup on 14 different times.
Paris Saint-Germain needed a dramatic leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be sailing towards a comfortable triumph in the match featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side fired twice late to take a surprise lead. First, the English forward converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a vital equaliser in the final moments to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to seal a convincing penalty victory.
Now 14-time 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 competition for the twelfth time in the past thirteen seasons.
