The Parisian club has now secured the prestigious cup on fourteen separate occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to overcome Marseille 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 Ligue 1 winners and the French Cup winners after Ousmane Dembele found the net early on.
However, the southern French side struck twice late to seize a shock advantage. Initially, the English forward converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial leveler in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to seal a convincing shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past 13 years.