On 11 February 2007, he played his first Serie A match after his Siena return, against Cagliari. Maccarone scored a brace in the 4–3 defeat against A.C. Milan on 17 February, to register his first goals for Siena. He finished the season with six goals, and added 13 in the following (club best by a long margin), as Siena achieved two consecutive 13th league places. After the club was relegated at the end of the 2009–10 season, Maccarone agreed a move to Sicilian Serie A club Palermo, signing a three-year deal with the "rosanero", for €4.5 million.