PSG has now secured the season-opening trophy on 14 separate times.
The Parisian giants needed a stoppage-time equaliser 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 coasting towards a comfortable win in the showdown featuring the Ligue 1 winners and the Coupe de France holders after the French winger found the scoring in the opening stages.
Yet, the southern French side fired two times in the closing moments to take a shock lead. Initially, the English forward scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a vital equaliser in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time winners 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 past thirteen seasons.
