PSG has now claimed the season-opening trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions seemed to be sailing towards a comfortable win in the match featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired two times late to seize a surprise lead. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos grabbed a crucial leveler in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 penalty win.
The record champions PSG, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the 12th time in the last 13 years.
