PSG has now won the prestigious cup on fourteen different occasions.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be coasting towards a straightforward win in the showdown between the French league champions and the French Cup winners after the French winger opened the net in the opening stages.
Yet, Marseille fired twice in the closing moments to seize a surprise advantage. Initially, the English forward scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial equaliser in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored successfully for PSG to complete a 4-1 penalty win.
The record winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past 13 years.
