A probe that began in February 2016, "resulted today in an operation to serve 185 arrest warrants, including 95 against military police," the Rio state security office said in a statement.
In Brazil, regular patrol officers are known as military police.
The sweep was carried out with "the unconditional" support of the military police internal affairs department and a special organised crime unit, the statement read.
Brazilian media reported that scores of drug traffickers were the other targets of the operation.
Security officials were to give a press conference later in Rio de Janeiro.