He was in charge of the Italy 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.

Due to his focus on defensive stability, as well as the presence of two pure, prolific goalscoring strikers, Riva and Boninsegna, Valcareggi felt that it would not be possible to field Italy's two most revered advanced playmakers at the time, Gianni Rivera, and Sandro Mazzola, alongside each other.

Following his international career, Valcareggi worked as a club coach in Italy with Hellas Verona and Roma, as well as the Italian youth B Team; he also briefly served as a pundit.

Valcareggi was also known for this infamous staffetta policy, which involved him using his two star, talented, and skilful playmakers – Mazzola and Rivera – for one half each during matches, so as not to offset the balance within the team.

The more athletic, dynamic, and direct Mazzola would start matches, while the more creative but less mobile and hard-working Rivera would come on when the opponents would begin to tire, which would allow him to dictate the game in midfield with his passing.