The Parisian club has now secured the prestigious cup on fourteen different occasions.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a straightforward win in the match featuring the French league champions and the French Cup winners after the French winger found the scoring in the opening stages.
Yet, the southern French side struck two times in the closing moments to take a shock lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker grabbed a vital leveler in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, saving crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for PSG to complete a 4-1 penalty win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past 13 seasons.