Sergio Cabral served two terms as Rio state governor from 2007 to 2014.
He was accused of received kickbacks from construction firms in return for awarding them lucrative contracts, such as a petrochemical plant in Rio.
Judge Sergio Moro said there was not enough evidence to convict Cabral's wife Adriana Ancelmo.
Cabral was detained in November as part of Operation Car Wash, a huge corruption investigation which has resulted in the arrest of a long list of high-ranking politicians and influential business people in Brazil.
Cabral is a member of the Brazilian Democratic Movement Party of President Michel Temer, who is also under investigation for alleged corruption.
Judge Moro said the former governor had taken 2.7m reais ($813,000; Â£638,000) in bribes.
The judge said the money had not yet been found and that he suspected Cabral had transferred it before his accounts were blocked.
The former interior minister for Rio state, Wilson Carlos Carvalho, was also found guilty of corruption and sentenced to 10 years in prison.
He was Cabral's right-hand man while he was in office.
The former governor of Brazil's Rio de Janeiro state has been sentenced to 14 years and two months in prison for corruption and money laundering.