In 2000, Cioni was selected for the team, alongside, amongst others, Filippo Pozzato, Fabian Cancellara, Michael Rogers and Charlie Wegelius. His intention was to use the training on the road to help his mountain bike career with the specific aim of riding for Italy at the 2000 Summer Olympics. However, he was not selected for the Olympics and it was at this point that Cioni decided to concentrate on road racing. In his first season, Cioni won a stage of the Tour of Slovenia and was second in a stage of the Tour de Normandie. He also rode his first Vuelta a España. In 2001, Cioni won his first stage race, the Vuelta Minho in Portugal. Cioni moved to in 2003, where he was used as a domestique for Alessandro Petacchi. Whilst Petacchi flourished that season, Cioni had no notable results.