"The RFEF regrets to announce that the central defender Diego Llorente tested positive in the last PCR tests carried out this morning at the concentration of the national team in Las Rozas," the federation said in a statement.
"The footballer will leave tonight the concentration of the national team in a medicalized vehicle, following all the established health protocols," it added.
Llorente is the second player of Spain's EURO 2020 squad after captain Sergio Busquets who tested positive for coronavirus.
The 27-year-old made seven appearances for the Spanish national team.