The victims were labourers picking Tendu leaves (used for making beedis) in the forest.
A forest department release said the incident took place in Alewahi area of Brahmapuri forest division, some 80 km from Chandrapur.
While the bear killed Ranjana Ambadas Raut (56), resident of village Kitadi, on the spot, Bisan Soma Kulmethe (45) and Farookh Yousuf Sheikh (31) died during treatment.
Veena Dudharam Raut (35), Kunal Dudharam Raut (16) and Sachin Bisan Kulmethe (25) were seriously injured as the animal attacked them.
Two other labourers climbed a tree to escape the ferocious animal, and were rescued only when a team of forest officials and police reached the spot.
After the Principal Chief Conservator of Forests granted permission to kill the bear, the police shot it dead.