Alba, who is set to complete a €14m move from Valencia for Barcelona later this week, played every minute in Poland and Ukraine as Spain retained their European Championship title. The left-back also scored Spain's second goal in Sunday's 4-0 final thrashing of Italy and was included in UEFA's team of the tournament.
Chelsea forward Mata netted Spain's final goal against the Italians after coming off the bench for his first appearance of the competition. Also named in Luis Milla's 22-man squad are four members of the Athletic Bilbao side that reached the finals of the UEFA Europa League and Copa del Rey last season, with Iker Muniain, Ander Herrera and Mikel San Jose joining Martinez.
Manchester United goalkeeper David De Gea, Barcelona playmaker Thiago Alcantara and Atletico Madrid forward Adrian Lopez - who won the Golden Boot as Spain claimed the Under-21 European Championship title last summer - are also included.
Those players have been called up for the friendly matches against Senegal (13 July) and Mexico (18 July) before the squad is reduced to 18 for the London Games.
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 Domínguez (Borussia Monchengladbach), Inigo Martinez (Real Sociedad), Javi Martínez 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)
(*Please note that squad lists only become official after they have been submitted to and announced by FIFA.)