PSG has now won the season-opening trophy on fourteen different times.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive Trophee des Champions title.
The European champions seemed to be coasting towards a straightforward win in the showdown between the French league champions and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, Marseille struck two times late to take a shock lead. First, Mason Greenwood scored from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a vital leveler in the final moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to seal a 4-1 penalty win.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the 12th time in the last 13 years.