Valcareggi is widely remembered for his success as a coach, in particular with Italy national football team. He began his coaching career as a player–manager with Piombino in 1952; after managing several Italian club sides (including Prato, helping the club to the 1956–57 Serie C title and Serie B promotion, as well as Atalanta and Fiorentina), he was named the Italian team's coach, replacing manager Edmondo Fabbri – under whom he served as an assistant – initially alongside Helenio Herrera, and later independently. He was in charge of the Italian national side between 1966 and 1974, guiding them to victory in the 1968 European Championship on home soil, and to the final in the 1970 FIFA World Cup in Mexico. Under Valcareggi, Italy lost only six games in eight years.