On 20 October 2009, he played his first game for Fiorentina, at UEFA Champions League 2009–10 versus Debreceni VSC, replacing Dario Dainelli at half time.

After the departure of Dainelli to Genoa in January, and the fitness problems of Alessandro Gamberini, Per Krøldrup and new signing Felipe, along with tactical rotation, he earned more chances to play, including the Champions league match against FC Bayern Munich.

[15] Natali scored his first goal for Fiorentina on 29 January 2012, netting the second in a 2–1 victory over derby rivals Siena.

[17] Along with his Atalanta teammate Gianpaolo Bellini, Natali was called up to the Italy under-21 squad for the 2002 UEFA European Under-21 Football Championship.

In March 2004, he made his only international appearance in the senior Italy national team, to replace injured Marcello Castellini.