PSG has now won the season-opening cup on 14 different occasions.
The Parisian giants required a dramatic leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions seemed to be sailing towards a straightforward win in the match featuring the French league champions and the Coupe de France holders after the French winger found the scoring early on.
Yet, Marseille fired two times late to seize a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a vital leveler in the dying moments to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all scored successfully for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time champions PSG, who met 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 twelfth time in the last 13 seasons.
