The Real Madrid captain has won 180 caps for his country and lifted the World Cup with them in 2010.
Ramos has also won the Euros twice with Spain, but he will not get the chance to add a third crown this summer after manager Luis Enrique left him out of his squad following an injury-hit season.
Enrique has named a 24-man group, despite Uefa allowing countries to pick 26, with not a single Real Madrid player representing La Roja at a major tournament for the first time in history.
Chelsea captain Cesar Azpilicueta has earned a recall and was a surprise inclusion in the 24-man group named by Enrique on Monday.
Blues goalkeeper Kepa Arrizabalaga has missed out, though, with Manchester United’s David de Gea and Robert Sanchez of Brighton getting the nod over him.
Leeds defender Diego Llorente, Liverpool midfielder Thiago and Wolves winger Adama Traore are also in the squad.
Spain’s Euro 2020 squad in full
Goalkeepers: David De Gea, Unai Simon, Robert Sanchez
Defenders: Aymeric Laporte, Jordi Alba, Jose Gaya, Pau Torres, Eric Garcia, Diego Llorente, Cesar Azpilicueta, Marcos Llorente
Midfielders: Sergio Busquets, Rodri, Pedri, Thiago, Koke, Fabian
Forwards: Dani Olmo, Mikel Oyarzabal, Alvaro Morata, Gerard Moreno, Ferran Torres, Adama Traore, Pablo Sarabia