The incident occurred shortly after midnight at a Central Reserve Police Force (CRPF) camp of 111 battalion in Aranpur village, some 60 km from Dantewada town and 440 km from the state capital Raipur.
The killer, Deep Kumar Tiwari, has been arrested, District Superintendent of Police Narendra Khare told IANS on telephone.
Tiwari was mentally disturbed and he opened fire on five of his colleagues without any reason, Khare said.
The dead men were identified as Chandan Singh, Ramesh, Purshottam and Aniruddha Singh.
Three of them died instantly while the fourth succumbed to his injuries on his way to hospital.
A fifth trooper was in critical condition and shifted to a government hospital in Jagdalpur town.
Aranpur village lies in a thickly forested area and is part of a region dominated by the outlawed Communist Party of India-Maoist.