The Napoli defender, 33, has made 34 appearances for the national team, most recently in a 1-0 friendly defeat to Spain in March 2014.
Maggio, part of the squad that reached the Euro 2012 final, confirmed the news in a press conference on Wednesday, as Napoli prepared for their UEFA Europa League last 16 second leg tie against Dynamo Moscow.
"It was a difficult decision for me because I have represented the national team for seven years but now I have decided to leave it," he said.
"In every football player's career comes the moment you must make these choices, the national team is a chapter closed.
"I experienced so many emotions with the national team and I thank them for all the joys of these seven years but it is a choice that I have taken after time."
Maggio's contract with Napoli expires at the end of the season, but the full-back refused to discuss any speculation surrounding his future, with rumours growing of a possible move to Inter.
"The renewal is not my priority, I just want to do well and get as far as possible in all three competitions," he added.
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