The 31-year-old AC Milan star, who played in the Champions League final win against Liverpool in May, want to concentrate on club commitments.
He said: "I will never join the national team again. My adventure with the Azzurri finishes here."
Nesta, who won 78 caps, was part of Italy's squad that won the World Cup in Germany in 2006.
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He is a great defender who I loved to watch on the International stage. His partnerships over the yeats with Cannavaro have been brillaint. I suppose this means that Materazzi will cement his position in the side from the next few years.
Whats the next generation of defenders like in Italy?