Despite finishing eighth in La Liga and reaching the semi-finals of the UEFA Europa League - losing to eventual winners Sevilla following an injury-time goal - new owner Peter Lim decided to relieve Pizzi of his duties on Wednesday.
And Valencia have wasted little time appointing a new coach, with Nuno to take charge on a one-year deal after guiding Rio Ave to Europa League qualification on the back of runners-up performances in both of Portugal's domestic cup competitions in just his second season at the helm.
The 40-year-old also has the option of extending his deal should Valencia succeed under his stewardship.
"Valencia have reached an agreement to contract Mr. Nuno Espirito Santo as manager, through to June 30th, 2015," a statement read on the club's website on Thursday.
"The deal includes the possibility of an additional year, based on sporting achievements. The 40 year-old Portuguese manager will be presented at the Ciudad Deportiva in Paterna at 12pm."
Nuno - a former goalkeeper for Deportivo La Coruna, Porto and Dynamo Moscow - helped Rio Ave reach the Taca da Liga and Taca de Portugal finals, only to lose to domestic powerhouses Benfica on both occasions.
