He is taking over from former assistant Robert Moreno, who coached the team through qualifying for the 2020 European Championship. His last match was on Monday, a 5-0 rout of Romania in Madrid.
Gerard Moreno scored twice for the hosts, who had already secured a spot in the tournament but needed the victory to be among the top-seeded teams in the draw this month.
David Villa on Wednesday announced that he would call it a day from professional football at the end of the season.
Ansu Fati, who made his debut with Barcelona this season, has quickly attracted everyone's attention and is already touted by many as the next big thing for the Spanish national team.
Luis Enrique stepped down as Spain's national team coach in June to be with his ailing daughter, who died a few days ago of a rare bone cancer osteosarcoma.
Saul Niguez and Thiago Alcantara also missed out on coach Luis Enrique's list announced on Friday for 2020 European Championship qualifying matches.
Raheem Sterling scored twice and Marcus Rashford once in a stunning first half leading England to its first win in Spain since 1987.
Luis Enrique first contact with players came less than two weeks ago in training camp. He immediately imposed his energetic style in the practice sessions, and it translated onto the field in the first two matches.
It was the biggest defeat ever for Croatia, who were playing their first competitive game since reaching the World Cup final in Russia.
The football fervor that swept through England during June and July was punctured by a 2-1 loss to Spain.
Pique had announced before the World Cup that he did not plan on returning to the national team after the tournament in Russia.
Enrique replaces Julen Lopetegui, who was sacked on the eve of the World Cup after accepting the job at Real Madrid.
Spain drew with Portugal and Morocco and beat Iran to get out of their group, but lost to Russia on penalties in the round of 16.
In four matches David De Gea managed to save just one shot on target from 11 he faced, including four from Sunday's penalty shoot-out.
Russia won a World Cup knockout game for the first time since the Soviet Union in 1966, defeating Spain 4-3 on penalty kicks after a 1-1 tie.
The World Cup's lowest-ranked team — 70th when the tournament began — now advances to a quarterfinal after causing one of the biggest upsets of the tourney, defeating Spain on penalties.
The 2010 World Cup champions Spain, have a tough task set up on the road to glory as they take on hosts Russia for a spot in the quarterfinals.
It was far from a beautiful win, but the Diego Costa goal was enough to make Spain coach Fernando Hierro smile.
Spain tied 3-3 with Portugal on Friday in their first World Cup 2018 match under newly-minted head coach Hierro.
As the first week of the World Cup is nearing its end, we analyse the main reasons behind the top team's debacle in their opening matches.
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