Azzini played for 5 seasons (152 games, 2 goals) in the Serie A for Calcio Padova.
Azzini is mostly remembered for being accused of fixing a game that his team Padova lost 0–3 to Atalanta B.C.
He maintained that the key witness, his ex-girlfriend Silveria Marchesini, was lying as revenge for him leaving her.
Azzini played his only game for the Italy national football team on 21 July 1952, against Hungary, during the 1952 Summer Olympics.
This biographical article related to association football in Italy, about a midfielder born in the 1920s, is a stub.