The Parisian club has now won the season-opening trophy on fourteen separate occasions.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele opened the net early on.
However, the southern French side fired two times in the closing moments to take a shock advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a vital equaliser in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 shootout win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
