Biava was confirmed by head coach Francesco Guidolin as a key player during the 2004–05 season, coincidentally his first season in the top flight, which ended with a historical first qualification for Palermo in the UEFA Cup. However, he did not confirm his performances in the following season, where he was mostly featured as backup player. With Guidolin back at the helm of Palermo in 2006–07, Biava regained a more important role in the Palermo squad, returning to play at his usual levels.