Police said the six were caught in an exchange of fire between security personnel and Maoists while they were travelling in an auto-rickshaw at Gumutmaha village in a dense forest area near Kuttamgarh under Tumudibandha police station jurisdiction last night.
Five of those caught in the cross fire died on the spot, while another person succumbed to injuries later, Kandamal superintendent of police Pinak Mishra told reporters.
The SP said acting on information about Maoist movement in the area, CRPF, Special Operations Group and district voluntary force (DVF) personnel had set up an ambush but the auto-rickshaw carrying the villagers came in between.
"It is unfortunate that the civilians were caught in the cross fire. Those killed included two women and a minor boy," he said, adding the circumstances in which the incident took place were being probed.
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Expressing deep concern over the incident, Chief Minister Naveen Patnaik ordered a judicial inquiry into it.
Meanwhile, irate local residents blocked Rayagada- Phulbani state highway protesting against the killing of innocent persons in the police-Maoist encounter.
Demanding a court-monitored probe by a special investigating team, the Campaign Against Fabricated Cases (CAFC), Odisha, blamed the police for the killing of people belonging to tribal and dalit communities in the incident.
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The chief minister also announced that the next of kin of the dead in the cross fire would be provided with government job.
Odisha PCC vice-president Pradeep Majhi hit out at the state government for the tragedy and dubbed it as "anti-tribal" and "anti-dalit."
Majhi, who was last month jailed over his agitation in Nabarangpur demanding tribal right over forest land, told a at a press conference in Rayagada alleged that similar incidents had also taken place in Kalahandi and Rayagada.
"The government has been targeting the tribals in the name of anti-Maoist operation," Majhi said and warned that a mass movement was taking shape against killing of tribals and dalits.