The Parisian club has now won the prestigious trophy on fourteen separate times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive Trophee des Champions title.
The European champions appeared to be coasting towards a comfortable triumph in the showdown between the French league winners and the French Cup winners after Ousmane Dembele found the net early on.
However, the southern French side fired two times late to seize a surprise advantage. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a crucial equaliser in the final seconds to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving decisive kicks from 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 victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this trophy for the 12th time in the last 13 years.
