The defender suffered pain during the friendly match with Italy on Thursday and will play no part in the upcoming clash with Romania on Thursday.
Sergio Ramos has withdrawn from Spain's squad for their friendly against Romania due to a back injury.
The Real Madrid captain was replaced at halftime of Spain's 1-1 draw with Italy on Thursday after struggling with the problem.
A statement from the Spanish FA read: "Sergio Ramos has left the national team's training camp on Friday morning due to a back problem that kept him out of the second half of the meeting with Italy.