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The incident took place at around 4.30 am, they said.
There was a blast in the receiver tank of the reactor at the pharmaceutical company located at Kharvai village in the Badlapur MIDC (Maharashtra Industrial Development Corporation), chief fire officer of the Kulgaon-Badlapur fire station, Bhagwat Sonawane, said.
There was also a subsequent fire in the reactor unit, he said.
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A metal piece from the blast site blew 300 to 400 metres away and fell on a house at a chawl (row tenement) in the village, injuring the occupants, the official said.
The victims were asleep when the metal piece fell on their house, pierced through the roof and fell on them with a high impact, he said.
A man staying in the house suffered severe injuries on his both legs and they had to be later amputated at a local hospital, a police official said.
His daughter too suffered leg injuries and his wife was also hurt. Both of them were treated in a local hospital, the police said.
The man was later shifted to the government-run JJ Hospital in neighbouring Mumbai for further treatment, Badlpur East senior police inspector Sukhada R Shitole-Shinde said.
Police were conducting a probe into the incident, she added.