Born in Sandrigo, Veneto, Pozzato turned professional in 2000 with the cycling team, part of the famous classe di '81 a group of emerging young riders born in 1981 who were part of the Mapei TT3 development team. Other alumni include Fabian Cancellara and Bernhard Eisel, Alexandr Kolobnev and Gryschenko.
After Mapei ended its sponsorship in 2002 Pozzato joined Giancarlo Ferretti's cycling team. Despite his win of Tirreno–Adriatico in 2003 and a stage win in the 2004 Tour de France, personality clashes with Ferretti meant that Pozzato suffered poor years with Fassa Bortolo in 2002–2004. During this period he was injured for some time and had to work for star sprinter Alessandro Petacchi at other times. During the 2004 season he was chosen to be part of the Italian 2004 Olympics team in support of team leaderPaolo Bettini who went on to win the event.
Quick Step–Innergetic
He re-established contact with several managers and directeurs sportif of. The Quick Step-Innergetic team expressed interest and Pozzato was able to obtain a release for the 2005 ProTour season, joining several former Mapei riders already on the team, such as Paolo Bettini and Davide Bramati. The 2005 ProTour season went better for Pozzato, with a win in the HEW Cyclassics in front of teammate Luca Paolini. The 2006 season saw him win the first major classic of the year Milan–San Remo after a superb ride which saw him first work for team leader Tom Boonen, but then was forced to launch his own winning attack in the finale.
Liquigas
For the 2007 season, Pozzato joined the Liquigas squad, and began his season in style, winning the Tour du Haut Var, the Omloop Het Volk and Stage 5 of the Tour de France.
Team Katusha
In 2009 he won the E3 Prijs Vlaanderen. His results show experience, comfort, and power on the cobblestones and on the Belgian hills. In aftermath of his 2nd place in the 2009 Paris–Roubaix, Pozzato claimed that when avoiding a crash of Thor Hushovd he lost 4 or 5 seconds and the chance for victory. He also suggested that Boonen benefited from the slipstream of official motorcycles to augment his lead. In 2010 he has been accused by several riders, including Bjorn Leukemans, Boonen and Philippe Gilbert for his "negative tactics" during key races. This resulted in the nickname "The Shadow".
Lampre-Merida
In 2013, Pozzato earned his first victory of the year in the Trofeo Laigueglia, held in Liguria, Italy on mainly narrow, twisting and turning roads. His team reeled in the breakaway and controlled the front of the leading group when Mauro Santambrogio attacked with to cover, with Pozzato jumping in his slipstream. The sprint was contested by 4 riders, Pozzato getting the best of them. This marked Pozzato's third win in the event, a record in the race's history. In September, he raced the GP Ouest-France and despite not being a top favourite, he won the race, becoming just the fifth Italian to do that.
In 2016 Pozzato joined the Italian-based Southeast Pro Cycling Team. In December 2018 he announced his retirement from competition.
Doping ban
In 2012, Pozzato was banned from cycling for three months by the Italian National Olympic Committee after it was found that he had worked with infamous doctor Michele Ferrari from 2005 to 2008. CONI had looked to ban him for a year but were forced to reduce it to a three months thanks to a technicality.