Zidane's departure from the role on Carlo Ancelotti's backroom staff was confirmed last month when he was confirmed as the new boss at Real Madrid Castilla, the European champions' reserve side.
Real released a statement on Thursday to confirm Hierro's appointment.
"Real Madrid CF would like to announce the addition of Fernando Hierro to the coaching staff as the first-team assistant coach, in replacement of Zinedine Zidane," it read.
Hierro made a staggering 601 appearances for Real during his 14 years at the club.
In that time, the Bernabeu outfit won three UEFA Champions League titles and five Liga crowns.
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