PSG has now won the season-opening cup on fourteen separate occasions.
Paris Saint-Germain required a dramatic leveler followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a record-extending fourth consecutive Trophee des Champions victory.
The European champions appeared to be sailing towards a straightforward triumph in the match between the French league champions and the Coupe de France holders after Ousmane Dembele found the net early on.
Yet, Marseille struck two times late to seize a shock lead. First, Mason Greenwood converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a vital equaliser in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to seal a convincing shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the past thirteen years.