PSG has now won the season-opening trophy on 14 different times.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and capture a record-extending fourth consecutive Trophee des Champions title.
The European champions appeared to be sailing towards a comfortable win in the match featuring the French league winners and the French Cup winners after the French winger opened the net in the opening stages.
Yet, the southern French side struck twice late to take a surprise advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital equaliser in the final seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to complete a 4-1 shootout win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last 13 years.
