Österreich-Rundfahrt
Born in Vittoria, Sicily, Napolitano turned professional in 2004 and for the 2004 and 2005 seasons he rode for the professional continental team . For the 2006 season he moved on to the UCI ProTour squad where his most important victories were two stage wins in the Tour of Austria, and a stage win in the Tour Méditerranéen. He joined at the beginning of the 2009 season.