The Parisian club has now claimed the season-opening cup on 14 different times.
Paris Saint-Germain required a dramatic equaliser followed by a successful 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 appeared to be coasting towards a straightforward win in the showdown between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the scoring early on.
However, the southern French side fired two times in the closing moments to take a surprise lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital equaliser in the final moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted successfully for Paris Saint-Germain to complete a 4-1 penalty victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last 13 years.
