The Parisian club has now won the prestigious trophy on 14 different times.
The Parisian giants required a dramatic equaliser followed by a successful penalty shootout to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The European champions seemed to be coasting towards a comfortable win in the showdown featuring the Ligue 1 winners and the Coupe de France winners after the French winger opened the net early on.
However, the southern French side struck two times in the closing moments to take a surprise lead. Initially, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial leveler in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing shootout win.
The record winners PSG, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the past 13 seasons.
