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. . Anzolin is most noted for having played most of the 1960s with Italian Serie A giants
Juventus, making 305 appearances (230 of which were in the league) with the club between 1961 and 1970. During his time at the club, he won a
Serie A championship during the
1966–67 season, as well as a
Coppa Italia during the
1964–65 season. He also won a minor international trophy with the club, the
Coppa delle Alpi, in 1963. With Juventus, he also reached the semi-finals of the
1967–68 European Cup, losing to Benfica. After his time with Juventus during the 60s and early 70s, he played for
Atalanta for a season in
Serie B, helping his club to gain promotion also thanks to a notable unbeaten streak of 792 minutes. He subsequently moved to
Lanerossi Vicenza as a second keeper, before ending his career at the age of 40, playing in
Serie C with
Monza,
Riccione, and
JuniorCasale, winning two consecutive "semi-professional" Coppa Italia trophies with Monza, between 1973 and 1975. After retiring, however, he was called upon by
Valdagno in the minor
Promozione League, to replace their sick goalkeeper, and he played 26 matches, conceding only 4 goals, at the age of 46. ==International career==