PSG has now won the season-opening trophy on 14 separate times.
Paris Saint-Germain required a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions appeared to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the Coupe de France holders after the French winger opened the scoring early on.
Yet, the southern French side struck twice in the closing moments to seize a shock advantage. Initially, the English forward converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a crucial leveler in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the last 13 seasons.
