The main battles in the first round of the nationwide polls are in Rio de Janeiro and Brazil's economic capital Sao Paulo, where the incumbent Workers' Party mayor, Fernando Haddad, risks being knocked out.
That beating for the left is expected to extend through much of the Latin American giant.
"The mayors' posts held by the Workers' Party will fall to less than half of those they won four years ago," political analyst David Fleischer at Brasilia University said, predicting "disaster for the party."
The polls also come just weeks after Dilma Rousseff of the Workers' Party was thrown out of the presidency in an impeachment vote over her illegal manipulation of public accounts.
She was replaced by her coalition partner and vice president Michel Temer from the center-right PMDB party, who is now pushing to steer Brazil away from 13 years of leftist economic policy.
Meanwhile, Rousseff's predecessor, Workers' Party founder Luiz Inacio Lula da Silva, faces charges in the Petrobras investigation. They could end the career of one of the most influential leftist leaders in recent Latin American history.
The latest victim was Jose Gomes da Rocha, running for mayor in Itumbiara in the state of Goias.
He was shot dead Wednesday, along with a police officer, while campaigning. The state's deputy governor was wounded in the attack in which the gunman was killed by security guards.
Supreme Court Chief Justice Gilmar Mendes called the incident "shocking."
Worries about violence have prompted deployment during the election of tens of thousands of troops to more than 400 municipalities, the defense minister said Friday.
"The police are prepared to secure the voting sites and to guarantee that everyone can exercise the right to vote," Colonel Luis Henrique Marinho Pires from police headquarters told the G1 news site.
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