It was the first time in the Argentine’s Barcelona career even though he has been sent off for his country twice in the past. One on his international debut against Hungary in 2005 and the other in the 2019 Copa America third-place play-off against Chile.
Having returned to the starting line-up after injury kept him out of the semi-final victory over Real Sociedad, Lionel Messi was dismissed after striking Asier Villalibre in the final minute.
The video assistant referee (VAR) spotted the incident as Messi, in his 753rd appearance for Barca was sent off for taking a swing at Asier Villalibre in the final seconds of extra time.
Messi had been heavily involved in a more positive way for Barcelona as they took the lead five minutes before the break.
Oscar De Marcos got on the end of a cross from Inaki Williams two minutes later to send the sides in level at half-time.
However, with 14 minutes left to play, French forward Antoine Griezmann scored what seemed to have been the clincher for the Catalans with a goal against the run of play but substitute Villalibre equalised for the hosts in the 90th minute to take the game into the extra period.
Athletic Bilbao’s forward Inaki Williams then curled a stunning effort into the far corner just three minutes into the additional half-hour to win the match for Marcelino Garcia’s side.
The victory brought a third Super Cup title for the Basque side and their first silverware since they claimed the same trophy in 2015 with a 5-1 aggregate win over Barca.
Athletic also reached new milestones, beating Real and Barca in consecutive games for the first time since 1960.