PSG has now won the season-opening cup on 14 different occasions.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a comfortable triumph in the match featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
Yet, Marseille fired two times late to seize a surprise lead. First, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial leveler in the dying seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial attempts from 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 seal a 4-1 shootout win.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
