PSG has now won the season-opening cup on 14 different times.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions seemed to be sailing towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele found the scoring early on.
However, the southern French side struck twice in the closing moments to take a shock lead. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker grabbed a crucial leveler in the final seconds to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to complete a convincing penalty victory.
Now 14-time winners PSG, who met 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 seasons.
