PSG has now won the season-opening cup on 14 separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and capture a fourth straight Trophee des Champions victory.
The European champions appeared to be sailing towards a comfortable win in the showdown featuring the French league winners and the French Cup holders after Ousmane Dembele opened the scoring early on.
Yet, the southern French side fired twice late to take a surprise lead. First, the English forward scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a crucial leveler in the dying seconds to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a 4-1 penalty victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this competition for the 12th time in the past 13 seasons.
