In 2006, Pezão was chosen by Sérgio Cabral Filho, then candidate to the governorship of Rio de Janeiro, to be his running mate.

They won the election and Pezão took office as Vice Governor and State Secretary of Public Works simultaneously.

He assumed the office of governor due to the resignation of Sérgio Cabral, that at the time had plans to run for the senate).

On 29 November 2018, after a request of the Prosecutor General of the Republic Raquel Dodge, accepted by the Justice of the Superior Court of Justice Felix Fischer, Pezão was arrested by the Federal Police in a new phase of Operation Car Wash, named Operation Werewolf (Operação Boca de Lobo).

[1] Pezão is accused of proceeding with corruption schemes that began during the government of Sérgio Cabral.