PSG has now secured the prestigious cup on 14 separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect penalty shootout to overcome Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the scoring early on.
However, the southern French side fired twice in the closing moments to seize a surprise advantage. Initially, the English forward converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos grabbed a crucial equaliser in the final seconds to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.
