PSG has now claimed the season-opening cup on 14 different occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a record-extending fourth consecutive Trophee des Champions victory.
The European champions appeared to be coasting towards a comfortable win in the showdown featuring the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele opened the net in the opening stages.
However, the southern French side struck two times in the closing moments to take a surprise lead. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial leveler in the final moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored successfully for PSG to seal a 4-1 penalty victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the last thirteen years.
