Paes, who, as Mayor, is the head of the Municipal Government which is a separate entity to the State authorities, particularly criticised their failure to deal with violent crime.
"This is the most serious issue in Rio and the state is doing a terrible, horrible job," he told CNN.
"It's completely failing at its work of policing and taking care of people."
This follows a tumultuous week during which striking police held up signs at the city's main airport welcoming tourists "to hell", before human body parts were washed-up on Copacabana Bay.