Under new head coach Siniša Mihajlović, Álvarez became a more valuable player in the squad following the departure of right back Gennaro Sardo, and eventually surpassed Alessandro Potenza for the starting right full back position. Álvarez made over 30 appearances for his Catania, in his return season, and was an undisputed starter for much of the season. He was noted for his big-team peak performances, as he notably kept Argentine star Diego Milito at bay in a 3–1 win for Calcio Catania over Inter Milan at the Stadio Angelo Massimino, as well as Ronaldinho in a 2–2 draw with A.C. Milan at the San Siro. Catania also notably defeated Juventus, in a season, that the team reached a record points total in the Serie A, finishing in 13th position, also making it to the semi-finals of the 2009–10 Coppa Italia. Catania reached a record points total for the third consecutive year during the 2010–11 Serie A season, and again for a fourth consecutive season during the 2011–12 Serie A campaign. During that campaign however, Álvarez was used in just 8 league matches by coach Vincenzo Montella, and on 31 January 2012, Álvarez was loaned out to La Liga club Real Zaragoza for the rest of the season. He made his debut for the club on 12 February 2012, and returned to Catania upon the expiration of his loan deal.