Costa had been set to represent his adopted nation in his homeland after a drawn-out tussle between Spain and Brazil over who he would play for.
The Atletico Madrid man played two friendlies for Brazil in March 2013, but made his Spain bow against Italy in February this year after making his decision.
And he will have the chance to do so after winning his race against time to recover from a hamstring injury.
The striker was withdrawn in the final game of his side's La Liga campaign as they drew with Barcelona to win the league.
Having been involved in a race against time to be fit for the UEFA Champions League final against Real, he was named in Diego Simeone's starting XI in Lisbon.
However, he lasted just nine minutes at the Estadio da Luz and subsequently was not named in Vicente del Bosque's squad for the friendly win over Bolivia on Friday.
Alvaro Negredo and Fernando Llorente are the strikers to miss out in Costa's selection, meaning Fernando Torres will travel to Brazil.
Del Bosque confirmed on Friday that Alberto Moreno and Ander Iturraspe would not make the cut, while Jesus Navas and Thiago Alcantara have seen injuries deny them their spot and Real Madrid full-back Dani Carvajal also misses out.
Spain begin their quest to retain the World Cup against 2010 final opponents Netherlands in Salvador before facing Chile and Australia in Group B.
Squad in full:
Goalkeepers: Iker Casillas (Real Madrid), David de Gea (Manchester United), Pepe Reina (Napoli)
Defenders: Jordi Alba (Barcelona), Raul Albiol (Napoli), Cesar Azpilicueta (Chelsea), Juanfran (Atletico Madrid), Gerard Pique (Barcelona), Sergio Ramos (Real Madrid)
Midfielders: Xabi Alonso (Real Madrid), Sergio Busquets (Barcelona), Santi Cazorla (Arsenal), Cesc Fabregas (Barcelona), Andres Iniesta (Barcelona), Koke (Atletico Madrid), Javi Martinez (Bayern Munich), Juan Mata (Chelsea), Pedro (Barcelona), David Silva (Manchester City), Xavi (Barcelona)
Forwards: Diego Costa (Atletico Madrid), Fernando Torres (Chelsea), David Villa (Atletico Madrid)
