In 2003–04, Biava marked his Serie B debut, and scored the goal which ensured the first AlbinoLeffe victory in the league, a 1–0 win against Fiorentina.

Biava immediately gained a place in the regular lineup, forming a defensive line together with Pietro Accardi and leading the rosanero back to Serie A after over 30 years.

During the summer 2007, Biava refused an offer from his childhood team Atalanta, preferring instead to stay at Palermo even though the club management could not ensure him a place as a regular.

In the first half of 2009–10 season he often partnered with Bocchetti but in January faced competition in new signing Dario Dainelli while the team's coach preferred a 3–5–2 formation with 3 central defenders and 2 wing-backs.

[4][5] Along with new signing André Dias, he became the backbone of the Lazio team starting in 11 matches in the second half of the 2009–10 season and helped the club survive the relegation battle.

[7] On 23 June 2022, AlbinoLeffe announced to have promoted Biava as head coach for the 2022–23 Serie C campaign, with former Giana Erminio boss Raul Bertarelli as his assistant.