After a negative 1962–63 season, in which he managed to score only a single goal in 18 Serie A appearances for Fiorentina, Milani was purchased by Inter, becoming a member of what would later be known as Helenio Herrera's "Grande Inter" side. Milani had a successful season with the Milanese club, scoring 7 goals in 18 Serie A appearances, helping Inter to a second-place finish in Serie A, narrowly missing out on the title after a losing a playoff match against the eventual 1964 Serie A champions, Bologna, who were tied on points with Inter for first place after the season's conclusion. Milani also won the 1963–64 European Cup with Inter that season, and he scored a goal in the 1964 European Cup final against Real Madrid. The following season, he followed up this triumph by winning the 1964 Intercontinental Cup with Inter against Copa Libertadores winners Independiente. During the winter of 1964, however, Milani was seriously injured in a European Cup match against Dynamo Bucarest, after getting kneed in the back. As a result of the collision, one of his vertebrae was displaced, thus ending his career prematurely. During his second season at Inter, he was still able to win a second European Cup, and the Serie A title, despite only playing in 11 matches, also reaching the Coppa Italia final with Inter.