Smith's exit follows the representative retirements of fellow Australian and Queensland greats Johnathan Thurston and Cooper Cronk announced past year, leaving a huge void for Walters to fill.
The 34-year-old has called time on his legendary career for Australia and Queensland, meaning he will not be available for selection in the 2018 State of Origin Series or any Kangaroos Test matches.
He captained Australia during the 2013 and 2017 World Cups, winning both.
"Today I'm announcing my retirement from representative football as of right now", he said in a statement.
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"It does not guarantee me any seasons in the NRL but I like to think it does give me an opportunity to stay on a bit longer".
"From a personal point of view I would have loved to have played on for a lot longer but unfortunately we don't live in a ideal world and those things don't happen", Smith said.
"Looking back on it now I just don't think that's fair for myself, I don't think that's fair on my family and also my teammates back here at Melbourne Storm".
Smith announced the surprise move on Tuesday afternoon that he would no longer play rugby league beyond his club duties with the Melbourne Storm.
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Maroons coach Kevin Walter said he had an inkling that Smith was wavering about Origin in their discussions through the year.
"A leader on and off the field and an inspiration to Queenslanders everywhere".
In his Origin career he missed just one game - the series opener in 2010 due to injury - and won a record 26 matches.
Smith, 34, is the most-capped State of Origin player in history, as well as the most successful racking up 11 series wins with the dominant Queensland side.
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Greg Inglis is widely seen as the most likely option to replace Smith as Queensland captain, with Inglis and NSW skipper Boyd Cordner in the frame to lead the national team.