Luis Enrique Martinez has been officially appointed the new coach of the Spanish national team.
Hierro has made a decision to "seek new horizons", according to the Spanish football federation (RFEF). Maintaining the typical Roja style while giving it an injection of energy will likely require the coach to refresh the line-up with the likes of Saul Niguez, Marco Asensio, and Rodri.
Under Hierro, 50, Spain were knocked out at the round-of-16 stage after losing to Russian Federation on penalties.
Enrique will also be taking over a team without key captain Andres Iniesta, who has retired from worldwide football. I like his commitment and he has turned down better paid jobs in order to coach Spain.
Luis Enrique had last been manager of Barcelona till 2017.More news: Colombia suffered 'monumental theft' against England, claims Maradona
Hierro was not expected to continue as coach after the World Cup but the RFEF has announced he will not stay with the organisation in any role.
Enrique has been out of management since leaving the Nou Camp last June.
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.
Luis Enrique has played for both Real Madrid and Barcelona, as well as managing Celta Vigo, Roma, and winning the Champions League with Barcelona in 2014/15.
A statement said the former Real Madrid player had "declined" to return to his previous role and has opted to "undertake new professional challenges".
Spain face England on September 8 at Wembley in their first game of the UEFA Nations League, after being drawn in a group which also contains Croatia.