Llorente, who Leeds snapped up from Real Sociedad in the international transfer window, is with the Spain squad and had been due to travel with the group to the Ukraine.
Spain are due to meet Ukraine in Kyiv, but Llorente will now not travel or be involved in the UEFA Nations League encounter.
The Spanish FA has confirmed that Llorente could not finish Sunday’s training session due to a muscular problem.
As such, Llorente will not travel to the Ukraine.
Leeds have been informed of the issue by the Spanish FA and will be keen to assess Llorente upon his return to Elland Road.
It remains to be seen whether the injury will force Llorente to miss any of Leeds’ upcoming matches.
Leeds can still sign players, with the domestic transfer window open until Friday, but have a number of other centre-backs available in the event Llorente is ruled out for a lengthy period.
