Anzolin made his professional debut with Marzotto Valdagno (1956–59) before moving to Palermo for two seasons. The club had purchased him for 40 million Lire, beating AC Milan by 5 million Lire, and offering him an annual salary of 5 million Lire. Before playing his final match of the 1960–61 Serie B season, he was informed of his transfer to Serie A winners Juventus, who signed him on a 14 million Lire contract. Palermo obtained Tarcisio Burgnich in exchange for their keeper, as well as Rune Börjesson on loan, and 100 million Lire.