PSG has now won the prestigious trophy on 14 different occasions.
The Parisian giants needed a stoppage-time equaliser followed by a successful penalty shootout to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable triumph in the match featuring the Ligue 1 champions and the French Cup winners after the French winger opened the net in the opening stages.
However, the southern French side struck two times late to take a surprise advantage. First, the English forward converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a crucial equaliser in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to complete a convincing penalty victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past thirteen seasons.
