Baroness Vadera is one of Gordon Brown's closes allies and advisers within the Treasury.
She will now become an adviser for the G20 from Downing Street.
Speaking at the United Nations in New York on Thursday, Mr Brown said he welcomed the news.
'The G20 is an increasingly important global group. The previous year has shown the vital importance of working together to deliver jobs, growth, and stability,' he said.
'In her new role Shriti will significantly strengthen the UK's engagement with the G20, including working with the Republic of Korea as the next chair.'
The news of her departure from the government comes during a particular difficult week for the prime minister.
Earlier this week, Labour MP Stephen Hesford stood down in the wake of the row over Baroness Scotland, the attorney general, and her hiring of an illegal immigrant.
Baroness Vadera developed an impressive reputation due to her handling of financial matter during the economic crisis.
Chancellor Alistair Darling joked earlier this year that the best way to deal with Britain's bankers who did not lend more was to: 'Put them in a room with [Vadera] and lock the doors for a couple of hours.'
She was created a life peer in 2007 and spent eight years in Treasury.
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