After four hours of voting the opposition in the lower house of Congress in Brasilia had reached 312 votes -- near its target of 342, or a two-thirds majority, which would send Rousseff to the Senate for the next stage of the process.
A senior leader of her Workers' Party said defeat was inevitable.
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"President Dilma (Rousseff's) government recognises this temporary defeat but that does not mean that the war is over," Guimaraes said. "The fight will continue in the streets and in the Senate."
The vote brought to a boil months of rancorous debate that has seen Rousseff's ruling coalition collapse and prompted huge street demonstrations.
The chamber's 513 deputies rose one by one to announce their vote at a microphone, greeted by cheers and sometimes jeering from the rest of the chamber.
Earlier, there were hours of debate regularly interrupted by chaotic scenes of deputies leading allies in patriotic anthems or singing parodies about the leftist Rousseff. Others chanted, waved large flags and one deputy even fired off a confetti cannon.
Brazil's first female president is accused of illegal government accounting tricks but, more broadly, is blamed for the country's worst recession in decades and galloping corruption.
The whole procedure was being aired live on television to the country of 204 million, the biggest in Latin America, and also on screens erected in city squares.
In Brasilia, about 53,000 pro-impeachment demonstrators massed outside Congress, according to a police count. About 26,000 turned out on the pro-Rousseff side, separated by a metal fence.
In Rio de Janeiro, which is scrambling to organise the Olympics this August, about 3,000 people each from the two sides demonstrated at separate time slots next to Copacabana beach.
So far, the atmosphere on the streets was peaceful, even festive, with a funk band singing in Rio and protesters blowing trumpets and vuvuzelas, as if at a football game, in Brasilia.
In Sao Paulo, the financial center, thousands of pro-impeachment supporters thronged the central Paulista Avenue, many of them in the country's green and yellow national football shirts.
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