Croatia join La Roja and the Three Lions in Group 3 of League A, the top tier of the new continental competition, reports Efe.
After the away clash with England, Spain is to host Croatia September 11.
Spain's respective return matches with England and Croatia are set for October 15 and November 15, respectively.
The Nations League will operate in years without World Cup and European Championship qualifiers and is intended to largely eliminate the need for friendlies.
The new tourney will also provide an alternate route to the playoffs for Euro Cup berths.
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