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On 13 August 2014, Martínez tore the ligaments on his left knee 30 minutes into the German Supercup encounter against Borussia Dortmund (eventual 0–2 loss), going on to miss the vast majority of the season.
At the age of 19 Martínez began appearing for Spain's under-21 team, representing the nation at the 2009 UEFA European Championships in Sweden, in a group stage exit.
In 2009–10 Martínez was the midfield engine of the team once more – 46 official matches, nine goals – and netted a career-best six times in the league campaign as Athletic narrowly missed on another UEFA Europa League qualification.
In the 2011–12 season, under new manager Marcelo Bielsa, he began being regularly used as a central defender.
Martínez played once in the final stages, replacing the injured Xabi Alonso for the final 20 minutes of the group stage 2–1 win against Chile on 25 June, as Spain emerged victorious in the tournament.