Nicknamed El Brujo (The Wizard) he played outside right for Deportivo de La Coruña, Real Madrid, and the Spain national team.

When Deportivo were promoted to first division, Amancio started to attract the attention of the scouts for major teams, such as Real Madrid.

Along with the signing of Amancio by Real Madrid in June 1962, players such as Ignacio Zoco, Lucien Muller and Yanko Daucik also arrived.

The ensuing season brought success for Madrid, as Miguel Muñoz added young players such as Pirri, Velázquez, Sanchís and Grosso.

Amancio drew level twenty minutes from the end, after collecting a signature pass, faking out a defender and skillfully booting the ball past the Yugoslav keeper Milutin Šoškić.

As a Real Madrid player, Amancio's reputation reached such international fame, that he had the honour of being called for a world team, promoted by FIFA.

With the team, he was a participant of one of its greatest achievements: winning the 1964 European Football Championship by a 2–1 score against the defending champions, the Soviet Union.

The team included the legendary Quinta del Buitre, made up of Butragueño, Míchel, Sanchis, Martín Vázquez and Pardeza.