The Parisian club has now secured the season-opening trophy on 14 separate 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 secure a fourth straight Trophee des Champions title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the match featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the net early on.
However, the southern French side fired two times late to seize a shock lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned 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 force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 penalty win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the last 13 seasons.
