In January 2008, however, Álvarez joined Sicilian giants Calcio Catania in the Italian Serie A, teaming up with former teammate Matias Silvestre, who also transferred to Catania in January 2008, from Boca Juniors. Under then-coach Silvio Baldini, Álvarez failed to make the imposed impact, and made just 6 league appearances in 5 months. Following the appointment of Walter Zenga, as the new head coach, Álvarez was set to remain at the club for the 2008–09 season, but failed to make an impact yet again, making just 6 additional appearances between August 2008 and January 2009, and thus, was sent out on loan to Rosario Central in order to gain more playing time and game experience. He signed for the Argentine club on 7 January 2009. During his loan spell, the player made 14 league appearances, and returned to Sicily on 30 June 2009.