US-trained Joaquim Levy will be replaced by current Planning Minister Nelson Barbosa, a close ally of Rousseff seen as less free-marketeering in his approach, her office said in a statement yesterday.
"The president is grateful for the dedication of Joaquim Levy, who played a fundamental role in tackling the economic crisis," it said.
Levy, 54, formerly worked at the International Monetary Fund and in Brazil earned the nickname "Scissorhands" for tough spending cuts in Latin America's biggest economy.
His departure comes just under a year after he took up the job of finance minister in the recession-hit country under Rousseff's leftist government.
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Her leadership is in crisis and she faces calls for impeachment proceedings in a public financing scandal.
The Supreme Court ruled Thursday that Congress must restart the impeachment proceedings from scratch, however, and overhauled the procedure in a badly needed win for the embattled president.
The political chaos is adding to Brazil's economic woes, with GDP down 4.5 percent in the third quarter year-on-year, and the national currency, the real, down one-third against the dollar this year.
He moved to reassure the country after being named as Levy's successor, promising to work for fiscal stability and growth and lower the inflation rate, which is currently more than 10 percent.
"We will promote fiscal balance, control of inflation and economic growth," he told a news conference.
He vowed also to work for longer-term fiscal reforms and control social spending.