Spain striker David Villa to miss Euro 2012
Villa, 30, fractured his tibia in December and told national coach Vicente del Bosque on Tuesday he will not be fit for the tournament.
He tweeted: "I've tried, but I can't be 100% to play the Eurocup. I called Del Bosque. It's the honest thing.
"Thanks to all of you for your support. I'll continue working to return as soon as possible with Barca and Spain."
Del Bosque, who names his final squad for the tournament on Sunday, had promised he would give Villa as long as possible to return to fitness.
A statement from the Spanish FA said : "Villa spoke with the national team coach this afternoon [Tuesday], after the team arrived in Schruns, Austria (for a pre-tournament training camp), Kazinform has learnt from BBC News.
"After not getting in the final practice and development desired, David Villa spoke with Del Bosque, who relayed that although it was Villa's wish to be with the team in Poland and Ukraine, that his physical state was 'not as good' as would be desirable."
Villa is Spain's record goalscorer, with 51 goals in 82 games.
Spain are also likely to be without veteran defender Carles Puyol, who is struggling with a knee injury, as they seek to defend the title they won in Vienna in 2008.
Spain won all eight of their qualifiers for Euro 2012 and are in Group C for the finals along with Italy, against who they play their opening game on June 10, Republic of Ireland and Croatia.