Spain manager Luis de la Fuente has called up four new players to his Spain squad that won the World Cup in July, as Barcelona duo Gavi and Joan Garcia were left out.
Espanyol forward Roberto Fernandez and Inter Milan goalkeeper Josep Martinez have received their first call-ups.
Real Madrid defender Dean Huijsen returns to the squad after missing out on victory in the US in July.
Fermin Lopez has also been selected by De la Fuente after injury prevented him from being part of the World Cup.
Garcia sustained a knee injury on Wednesday night, and Barcelona have not provided a return date for their goalkeeper.
Gavi would have missed the first game of the Nations League had he been selected, as he serves a one-game suspension for unsporting behaviour during the World Cup final.
Celta Vigo forward Borja Iglesias was the third player from the World Cup squad to miss out, while Marcos Llorente has retired.
Spain take on England at Wembley to start their Nations League campaign, followed by ties with Croatia, the Czech Republic and then Croatia again during the upcoming international break.
