PSG has now claimed the season-opening cup on 14 different times.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders seemed to be sailing towards a straightforward triumph in the match between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the net early on.
Yet, the southern French side struck twice late to take a surprise advantage. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial leveler in the dying moments to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored successfully for PSG to seal a convincing penalty win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this trophy for the 12th time in the past thirteen seasons.
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