Spain defender Raul Albiol fractured a cheekbone in training on Sunday and is out of Tuesday's Euro 2012 qualifier against Scotland in Alicante.
The Real Madrid centre-back had a scan that confirmed the fracture and has left the national team's training camp, Real said in a statement on their website.
The Spanish club did not say how long he might be sidelined.
Midfielder Xabi Alonso, Albiol's Real team-mate, trained normally in Sunday's evening session despite sustaining a gashed shin in Friday's 2-0 win against Czech Republic.
"Alonso trained without any apparent discomfort and said he felt fine, although he was wearing a large bandage on his right leg," the Spanish football federation (RFEF) said on its website.
Full-back Sergio Ramos, another Real player, trained apart from the rest of the squad after being substituted at half-time in Prague as a precaution but should be back with his team mates for Monday's session in Alicante, the RFEF added.
Spain, the world and European champions, qualified for the Euro 2012 finals in Ukraine and Poland with two games to spare and top Group I with a perfect 21 points from seven matches.
With one game to play, Scotland are second on 11 points and a win against Spain would secure them a play-off berth. Czech Republic, who play in Lithuania on Tuesday, are third on 10.comments