No less than 64 people died in a security raid against the Red Command gang in the Brazilian city's northern suburbs - the biggest and most lethal operation in the area's records.
Four law enforcement personnel were among those killed during Operation Containment in the communities of Alemão and Penha, local authorities said. More than 80 people were taken into custody.
Fierce clashes commenced when around 2,500 law enforcement officers entered the area on Tuesday early hours. The criminal organization responded with armed resistance, setting fire to barriers and using drone-dropped explosives, officials confirmed.
The United Nations human rights body stated it felt "horrified" by the security action, calling for "prompt and effective investigations".
The slum neighborhoods near the aerial transportation hub is seen as the headquarters of among the nation's strongest organised crime groups.
State officials stated no less than 50 of those killed were "indicated by police as suspected of being criminals".
Many residents were injured, including civilians caught in the crossfire.
Residents have described the mountainous region - inhabited by approximately 300,000 individuals - to a "war zone" since the raid started.
Transport routes stay blocked in the entire neighborhood.
The Red Command group has been increasing their influence in the area, increasing drug trafficking routes and power in the informal settlements.
Rio's police stated over 200kg (441lb) of illegal substances were seized in the operation, along with dozens of firearms.
The coordinated mission by various security forces comes after a year-long investigation.
Numerous alleged criminals are considered participants in an organization from the Pará state who are at the moment taking refuge in the metropolitan area.
Large-scale police operations are regular in the country before major international events in the South American nation.
The UN climate summit the environmental summit is taking place in the northern urban center in November.