D'Alessandro won the 2001 Under-20 World Championship with the Argentine youth side, held in Buenos Aires; due to his performances alongside his club teammate Javier Saviola, he was awarded the Silver Ball as the tournament's second best player. D'Alessandro had originally started the tournament as a substitute, but injuries in the team allowed him a place in the team during the later games. José Pekkermann give him the key to lead the Argentinian attack and the accounting with Javier Pedro Saviola Who Was great technical and mobility skills helps Argentina to won the title after beating Ghana 3–0 in the final. He has represented Argentina's senior side on 28 occasions, scoring 4 times between 2001 and 2011. He also represented Argentina's under-23 side at the 2004 Olympic Games in Athens, where Argentina won a gold medal.