Spain coach Julen Lopetegui was sensationally sacked on Wednesday, two days before their opening World Cup match against Portugal.
The country's federation said he failed to tell them he had agreed to join Real Madrid after the tournament.
Real unexpectedly announced on Tuesday that Lopetegui, who had only recently extended his contract with Spain and was unbeaten in his 20 games in charge, would take over as their coach next season.
In announcing the decision, the head of the Spanish football federation (RFEF) Luis Rubiales said Lopetegui's replacement would be announced "soon".
Rubiales said the federation had found out about Lopetegui's move five minutes before it was announced by the Champions League winners.
"I don't feel betrayed, the problem is that things have been done with the complete absence of the RFEF, which is something (we) cannot let go by."
Spain, one of the pre-tournament favourites and winners in 2010, also face Morocco and Iran in their group in Russia.
Rubiales added there were no hard feelings towards Lopetegui, who replaced Vicente del Bosque following Euro 2016.
"We want to thank Julen for all he's done and he's a big reason behind us being in Russia, but we feel obliged to dispense with his services," he said.
"There has to be a message to all RFEF employees and there are ways of behaving that you need to abide by."