The Parisian club has now won the prestigious cup on fourteen different times.
Paris Saint-Germain required 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 European champions seemed to be coasting towards a comfortable win in the showdown featuring the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side fired twice late to seize a surprise lead. Initially, the English forward scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of events, the Portuguese striker snatched a vital leveler in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a 4-1 penalty win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last 13 years.
