PSG has now claimed the prestigious cup on 14 different occasions.
The Parisian giants needed a dramatic equaliser followed by a successful 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 sailing towards a straightforward triumph in the match between the Ligue 1 winners and the French Cup winners after the French winger opened the scoring early on.
However, the southern French side struck two times in the closing moments to take a surprise advantage. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a vital leveler in the final moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the last thirteen seasons.
