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Mr Chauvel, a List MP, said he had resigned effective from March 11.
He will work for the UN Development Programme organisation former Prime
Minister Helen Clark leads - as an advisor on Parliamentary Development
and Democratic Governance.
Mr Chauvel said Ms Clark was not involved in his selection - "I don't think she even knows I have the job."
He said he had been a member of the UN Global Commission on HIV and the
Law for the past two years and had found that work challenging.
"The new full-time role with the UN presents a similar opportunity to
make a difference and I look forward to the challenges that it will
Former MP Carol Beaumont is next on Labour's list - followed by Kelvin Davis.
Labour leader David Shearer said Mr Chauvel had played an important role within Labour and would be missed.