[5] The following year, Pozzato won the final stage of the Giro della Liguria in February,[8] before repeating his victory at the Trofeo Laigueglia.

Personality clashes with Giancarlo Ferretti meant that Pozzato suffered poor years with Fassa Bortolo,[2] and thus, re-established contact with several managers and directeurs sportif of Quick-Step–Innergetic.

[17] His only other victory of the 2006 season came at the Tour of Britain, where he won the third stage of the race into Sheffield, having attacked from a six-rider lead group after the final categorised climb.

[5] In his first European start of the 2008 season, Pozzato won the opening stage of the inaugural Giro della Provincia di Grosseto in February, going on to win the general classification at the race as well.

Liquigas won the opening team time trial stage and with Pozzato crossing the finish line first, he assumed the gold jersey of race leader.

[33] Having finished second to Francesco Ginanni at February's Trofeo Laigueglia, Pozzato's first victory with Team Katusha came the following month at E3 Prijs Vlaanderen, winning a three-rider sprint against Tom Boonen and Maxim Iglinsky.

[37] In June, Pozzato won the Italian National Road Race Championships for the first time in his professional career, prevailing in a sprint finish of around 20 riders at the Imola Circuit.

[48] The following year, Pozzato was part of the lead group at Milan–San Remo; he chased down Philippe Gilbert's attack in the final 2 kilometres (1.2 miles), but this effected his ability to sprint at the end, ultimately finishing in fifth place.

In the spring classics, Pozzato took four top-ten results – two of which where he finished as part of the lead group – with a best of second place coming at the Tour of Flanders, where he was outsprinted by home rider Tom Boonen.

[55] He then won April's GP Industria & Artigianato di Larciano from a small group,[56] but this would turn out to be his only win of an injury-blighted season.

[57][58] He was also suspended for three months, backdated to June, for his links to Michele Ferrari, who had been given a lifetime ban from the sport earlier in the year.

His Lampre–Merida team reeled in the breakaway and controlled the front of the leading group when Mauro Santambrogio (Vini Fantini–Selle Italia) attacked with 3 kilometres (1.9 miles) to cover, with Pozzato jumping in his slipstream.

[73] In 2012, Pozzato was banned from cycling for three months by the Italian National Olympic Committee (CONI) after it was found that he had worked with infamous doctor Michele Ferrari from 2005 to 2008.