PSG has now secured the prestigious trophy on fourteen separate times.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The European champions seemed to be coasting towards a comfortable triumph in the showdown between the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side struck twice in the closing moments to seize a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a crucial leveler in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to complete a convincing shootout win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the last 13 years.
