PSG has now claimed the season-opening trophy on 14 separate occasions.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions seemed to be sailing towards a comfortable triumph in the match between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
Yet, Marseille struck two times in the closing moments to take a shock lead. Initially, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital leveler in the final moments to force the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted successfully for PSG to seal a convincing shootout win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.
