Hierro has chose to "seek new horizons", according to the Spanish football federation (RFEF).
A great number of tasks are at hand for Luis Enrique when he begins life as the coach of the Spanish national team, with a select number dominating the fate of his tenure.
"After many kilometers of walking together, the Royal Spanish Football Federation and Fernando Hierro put an end to their relationship once the participation of Spain in the World Cup in Russia has ended".
Spain subsequently qualified from the group stage but went out to hosts Russian Federation at the last-16 stage following a penalty shoot-out in Moscow.
The federation, fearing a split between players from Barcelona and Real, sacked Lopetegui two days before Spain's opening game against Portugal.
The new manager faces the same two-pronged brief that Lopetegui was tasked with two years ago: to restore confidence and get fresh blood from the younger generation. Hierro, who had previously held that role, decided not to return to the post following the World Cup.
"Luis Enrique comes with his staff, but he will speak about that topic next week".
It means those left from the triple triumph of Euro 2008, the 2010 World Cup and Euro 2012 will either be gone or down to the last few and that could pave the way for an evolution of style. He followed it up with a domestic double in the 2015-16 campaign.
He also coached Celta Vigo and Barca's reserve team and has spent the past year on sabbatical since leaving the Nou Camp in June 2017.
Molina, 47, is a former Spanish national goalkeeper and also played for Atletico Madrid and Deportivo de la Coruna.