The Parisian club has now secured the season-opening cup on fourteen different occasions.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight Trophee des Champions title.
The Champions League holders appeared to be coasting towards a straightforward win in the match between the Ligue 1 winners and the Coupe de France winners after the French winger found the scoring early on.
However, Marseille fired twice in the closing moments to seize a shock lead. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a crucial equaliser in the final seconds to send the contest into a deciding shootout. PSG goalkeeper 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 with composure for PSG to complete a 4-1 penalty win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the past 13 seasons.
