PSG has now claimed the prestigious trophy on 14 different times.
The Parisian giants needed a dramatic leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a straightforward triumph in the showdown between the French league winners and the French Cup holders after the French winger found the net in the opening stages.
However, the southern French side fired twice in the closing moments to seize a shock advantage. Initially, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital leveler in the dying seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 penalty victory.
The record winners 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 years.
