The Parisian club has now claimed the prestigious trophy on fourteen separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and capture a fourth straight Trophee des Champions title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown between the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the net early on.
However, the southern French side fired twice late to take a surprise advantage. First, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital leveler in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to complete a 4-1 shootout win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past 13 seasons.
