PSG has now won the season-opening cup on 14 different times.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful penalty shootout to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the match between the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side fired twice in the closing moments to take a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos grabbed a vital equaliser in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored successfully for PSG to seal a convincing shootout victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.