His career peaked whilst playing for Fiorentina between 1999 and 2001; although he was not given many league starts, he did start in three Champions League games for the Italian side. Bressan's main fame comes from one of these games, in the 3–3 group stage draw against Barcelona on 2 November 1999. After 14 minutes he scored what is considered one of the greatest goals of all time, a spectacular 25 yard bicycle kick. An ITV programme on the 50 greatest Champions League goals had it at number 2, behind Zinedine Zidane's title-winning volley against Bayer Leverkusen in the 2002 Champions League Final. Sky One also placed this goal as number 8 in their list of the 50 greatest Champions League goals. In the very same game against Barcelona, Bressan combined well with Abel Balbo, providing a spectacular backheel pass to assist Balbo in scoring Fiorentina's second goal of the game. His only league goal in the 1999–2000 season came during a 0–4 away victory against Inter Milan on the penultimate matchday.