The 40-year-old has moved to strengthen his coaching team with the well-respected Spaniard who enjoyed a successful spell at Mestalla previously with Rafael Benitez
Valencia coach Gary Neville has confirmed former Liverpool assistant Pako Ayestaran will be joining his background staff from Monday.
Neville enjoyed his first Liga win in charge of Valencia on Saturday night as his side came from behind to beat Espanyol 2-1 at Mestalla.
Goals from Alvaro Negredo and Denis Cheryshev gave the host all three points after Oscar Duarte had put Espanyol ahead.
Speaking after the match, Neville confirmed that Ayestaran would return to Valencia as assistant coach although he stressed the 53-year-old would not be replacing any of his current staff.