The French defender will not travel with the squad to Bilbao for Friday's encounter as he has been left out for tactical reasons
The Frenchman, who joined Barca from Valencia in the summer of 2014, was a key figure for the Camp Nou side last term as they won the treble, making 41 appearances in all competitions.
Mathieu also featured for the full 120 minutes in Barcelona's 5-4 European Supercup win over Sevilla on Tuesday, yet Luis Enrique does not need him for Friday's encounter at San Mames.
Meanwhile, Barcelona will also still be without Neymar, Douglas and Jordi Alba due to health issues and injuries, while new arrivals Aleix Vidal and Arda Turan will not be available until January.
"Neymar, Douglas and Jordi Alba are still unfit and have stayed in Barcelona," a statement on the club's official website reads.
"Arda Turan and Aleix Vidal are illegible, while Mathieu and Masip have also been left out."
Barcelona will be looking to win their fifth trophy of 2015 against Athletic as they have set their sights on winning the sextuple this calendar year.
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