PSG has now claimed the season-opening trophy on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a straightforward triumph in the match between the French league champions and the Coupe de France holders after the French winger found the net in the opening stages.
Yet, the southern French side fired twice in the closing moments to seize a surprise advantage. Initially, Mason Greenwood scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker grabbed a crucial leveler in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted successfully for PSG to seal a 4-1 penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the past 13 years.
