PSG has now secured the prestigious cup on fourteen different occasions.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a straightforward win in the match featuring the Ligue 1 champions and the French Cup winners after the French winger found the scoring early on.
However, the southern French side fired twice in the closing moments to seize a shock lead. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a vital equaliser in the dying moments to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past 13 seasons.
