Under the former Real Madrid and Spain defender, who had little previous coaching experience, 2010 winners Spain lost on penalties to host nation Russian Federation in the last 16.
But if you think really hard you might remember that on the eve of the tournament Spain chose to sack Julen Lopetegui.
Spanish football federation (RFEF) confirmed the development on Sunday afternoon.
Rubiales also said before Luis Enrique's appointment that Spain's players had no say in who the new coach would be.
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Despite been out of work since quitting the Nou Camp outfit, the 48-year-old football tactician has been linked with Arsenal after Arsene Wenger resigned at the end of last campaign.
Spain, who won back-to-back European titles (2008, 2012) and the 2010 World Cup, are hoping to open a new successful chapter under Luis Enrique after three consecutive disappointing tournaments.
Hierro had previously said he accepted responsibility for the team's failure to advance any further in the World Cup.
"Luis Enrique comes with his staff, but he will talk about that next week".
With Spain, Enrique will be aided by Jose Francisco Molina, 47, a former goalkeeper at Atletico Madrid and Deportivo La Coruna who played nine times for Spain and was named as sporting director.