PSG has now won the season-opening cup on 14 different times.
The Parisian giants required a dramatic equaliser followed by a successful 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 triumph in the showdown featuring the Ligue 1 champions and the French Cup holders after the French winger found the net in the opening stages.
Yet, Marseille fired twice late to take a surprise advantage. First, the English forward scored from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a vital leveler in the final moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored successfully for PSG to complete a 4-1 penalty victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
