The Senate voted 59 to 21 Wednesday in favor of impeachment trial proceedings.
The vote means Rousseff, who was suspended this year on allegations of breaking budget laws, will likely face trial later this month after the closing ceremonies of the Summer Olympic Games in Rio. The Games end on August 21.
The trial will take place in the Senate, presided over by the president of Brazil's Supreme Court.
The impeachment trial would convict or acquit Rousseff of committing the crime of "fiscal irresponsibility" for authorizing public bank credits in the budget to cover up budget deficits.
Vice President Michel Temer
stepped in as acting President and will take over permanently if Rousseff is impeached.
Rousseff, the country's first female President, has described her suspension as "a coup."
"I'm the victim of a great injustice," she said in May. While she is accused of breaking budget laws, she maintains she did the same things previous Brazilian leaders have done.
"I have made mistakes, but I have not committed any crimes. I am being judged unjustly, because I have followed the law to the letter," she said.
Rousseff vowed to keep fighting efforts to impeach her, and called for her supporters to join her.
"Destiny has reserved many challenges for me... Some of them seemed impossible to overcome. I have suffered from torture, I have suffered from sickness, and now I suffer from the pain of injustice," she said. "What is more painful now is injustice. I am victim of a political farce. But I won't give up. I look back and I see all we have accomplished. I look forward and I see all we still need to do."