Nereo Rocco took Milani to Padova, and the Italian striker formed a notable attacking partnership with Crippa, scoring 18 goals. In the summer of 1961, the president of Fiorentina, Longinotti, acquired Milani to strengthen his front-line, which featured the likes of Gianfranco Petris and Hamrin, who helped the team to capture the 1960–61 European Cup Winners' Cup and the Coppa Italia. In his first full season with the club, Milani initially went scoreless in Serie A for the first five matches, but on the sixth match-day of the 1961–62 Serie A season, on 24 September 1961, Milani scored two goals in a 5–2 home win over Udinese. This match is also remembered as being the debut of the legendary Italian goalkeeper Dino Zoff, therefore the first two goals that he conceded in his career were scored by Milani. With 22 goals, Milani finished the Serie A campaign as the joint Serie A topscorer, alongside Scudetto winner José Altafini, helping Fiorentina to a third-place finish in the league. Milani also helped Fiorentina to another European Cup Winners' Cup final that season.