Videos posted on the Internet showed the force of the explosion and the heat wave it produced setting aflame several fire trucks that were rushed to the scene on Tuesday morning.
"Everything is on fire," a voice in one of the videos posted on YouTube said.
A fireman wearing a silver heat-resistant suit and masks was seen running away from the spot of the disaster for safety.
"Everyone — leave. Whoever is still here — leave," one fireman said in a video.
Interior Minister Arsen Avakov said the initial explosion hit a fuel depot near the Vasylkiv village some 30 kilometres (20 miles) southwest of Kiev.
"Gigantic. Firemen have died," Avakov tweeted.
His later Twitter updates said several firemen initially presumed to have died had been pulled out alive from the flames.
A spokesperson for Ukraine's Emergencies Ministry told AFP that it was aware of six people being injured.
Kiev has been suffering from a dry heat spell for more than a week. But there was no initial information about what might have caused the blast.
The fuel depot hit by the initial explosion is owned by a Ukrainian company called BRSM-Nafta that operates a chain of filling stations.
The nearby filling station firm called KLO said it was also evacuating its staff from the scene. "The danger is real," KLO co-owner Vyacheslav Steshenko told the Interfax-Ukraine news agency.
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