Costa has been hobbled for weeks by a right thigh muscle problem, but coach Vicente del Bosque is prepared to gamble that the Atletico Madrid forward will be fit to lead the defending champions' attack.
Costa, who is a Brazilian-born Spanish national, is expected to start ahead of Fernando Torres and David Villa, who were also in the squad.
As expected, winger Jesus Navas was left out while Juan Mata was included despite a mixed Premier League season.
Sixteen of the 23 squad players who lifted the World Cup four years ago return for Spain.
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Del Bosque seemed to choose players like Mata and Torres on favour rather than obvious merit heading into Brazil, with Real Madrid playmaker Isco among those discarded. Bayern Munich midfielder Thiago Alcantara was unavailable due to injury.
While Costa's inclusion was hardly shocking, Del Bosque's decision to base Spain's attack around a forward who has been nagged by a hamstring problem over the final two months of the season is surprising considering his options.
Del Bosque said Friday after Spain's 2-0 friendly win over Bolivia that he has faith in Torres, who scored just five Premier League goals this season. David Villa, the country's all-time leading scorer, has seen his production dip but can easily slide into Spain's possession-based combination game, with midfielder Cesc Fabregas expected to reprise his role as an unorthodox striker when needed. Pedro Rodriguez was also named.