PSG has now claimed the season-opening cup on 14 different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a comfortable win in the showdown featuring the French league winners and the Coupe de France winners after the French winger found the scoring in the opening stages.
Yet, the southern French side struck two times late to seize a surprise advantage. First, the English forward scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial leveler in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 penalty win.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past 13 seasons.
