The RFEF's executive committee met on Monday and unanimously approved Luis Enrique's appointment just eight days after the national team, under caretaker manager Fernando Hierro, were eliminated on penalties by hosts Russian Federation in the second round of the World Cup.
Spain subsequently qualified from the group stage but went out to hosts Russian Federation at the last-16 stage following a penalty shoot-out in Moscow.
Unveiling the country's new manager, Luis Rubiales, the president of the Spanish Football Federation, said: "The decision has been unanimous, I like his commitment, he has missed out on better economic opportunities to manage Spain".
Fernando Hierro has stepped down as Spain coach. Andres Iniesta remains the only one to retire in the aftermath of that game, making Pique's predicament more pertinent with each passing day.
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Spanish football federation (RFEF) confirmed the development on Sunday afternoon. Hierro, who had previously held that role, decided not to return to the post following the World Cup.
The 48-year-old won two La Liga titles and the Champions League with the Catalan side before stepping down last year.
Former Barcelona boss Luis Enrique is set to be named as Spain's new manager.
A formal unveiling of Enrique is likely to happen next week and Rubiales said: 'We have not spoken to anybody else - only Luis Enrique'.
Roberto Martinez, who has led Belgium to the semi-finals of the World Cup, is among the coaches to have been linked with taking the Spain role.