The national team's then sporting director Fernando Hierro stepped in to replace him and led Spain to the last 16 where they lost to hosts Russian Federation on penalties, before stepping down after the tournament.
Hierro announced on Sunday that he would not be continuing as Spain manager, or returning to his post as sporting director.
Luis Enrique is favourite to take over as Spain manager.
Luis Rubiales, head of the Spanish FA, will reportedly suggest appointing Luis Enrique as the new boss in a meeting on Monday morning, although Roberto Martínez and Quique Sánchez Flores have also been considered as potential candidates.
The Royal Spanish Football Federation (RFEF) have scheduled a news conference on Monday to announce changes to the organisation's structure.
Croatia ends Russia's run, advances to World Cup semifinals
Croatia's victory will see them take on England in the semi-finals of the World Cup on Wednesday. The Villarreal left winger launched a 25-yard shot that nestled into the top-left corner.
A team with a history of success, a talented squad and a distinctive style of playing, had just failed to win a trophy for the first time in six years.
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.
"I don't think you can talk about the team breaking down or collapsing.
We liked his commitment and he has turned down better paid jobs to coach the Spanish national team".
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.