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The man, who reportedly identified himself as a policeman, took 37 people hostage on a bus that was travelling across a busy bridge connecting the suburb of Sao Goncalo to central Rio on Tuesday morning.
Several hostages who were released during negotiations recalled how the man had poured petrol in the vehicle and had threatened to set it alight.
After a four-hour standoff and negotiation, in which police say the hijacker made no specific demands, Brazil's elite police force BOPE said its sniper had "neutralised" him.
It added that all the hostages were released unharmed.
Rio bus hijacking: Hostages released after police sniper shoots hijacker dead
Some of the released hostages said the man had poured petrol in the bus and threatened to set it alight.
news.sky.com