Mata and Alba scored in Spain's 4-0 victory over Italy in the Euro 2012 final as Spain became the first European team to defend its title after winning the World Cup.
Coach Luis Milla named 22 players but will trim the team to 18 for the London Games, which begin this month.
Mata's Chelsea teammate Oriol Romeu was also included in the team, as was Manchester United goalkeeper David de Gea.
Milla called on four players from Athletic Bilbao, including Martinez, Ander Herrera and Iker Muniain. All three players, plus Barcelona's Thiago Alcantara - also in the squad - helped Spain's Under-21 side win the European Championship last season.
Martinez and Mata were also in Spain's squad when it won the World Cup two years ago. Alba was the only regular at this summer's European Championship, with Mata and Martinez making an appearance each.
Spain squad for London Olympics:
Goalkeepers: David De Gea (Manchester United), Diego Marino (Villarreal), Joel Robles (Atletico Madrid)
Defenders: Jordi Alba (Valencia/Barcelona), Cesar Azpilicueta (Marseille), Alberto Botia (Sporting Gijon), Alvaro Dominguez (Borussia Monchengladbach), Inigo Martinez (Real Sociedad), Javi Martinez and Mikel San Jose (both Athletic Bilbao), Martin Montoya (Barcelona)
Midfielders: Thiago Alcantara and Cristian Tello (both Barcelona), Ander Herrera (Athletic Bilbao), Isco (Malaga), Koke (Atletico Madrid), Juan Mata and Oriol Romeu (both Chelsea)
Forwards: Adrian Lopez (Atletico Madrid), Iker Muniain (Athletic Bilbao), Rodrigo (Benfica), Alvaro Vazquez (Espanyol).