The rebels triggered a land mine blast in the forested Gadchiroli area in Maharashtra state as the vehicle was passing through, police officer Sharad Shelar said.
Sheler said this could be a revenge attack by the rebels after security forces killed 37 insurgents in two separate gunbattles in the region in April last year.
Maharashtra state minister S. Mungantwar said the ambush was a desperate attack by the rebels because authorities had succeeded in holding peaceful voting for national elections in the area last month. The rebels had asked people to boycott the polls.
The Press Trust of India said the rebels first struck early Wednesday by burning more than 20 vehicles of a road construction company. They hid in the forest and targeted police commandos when they came searching for them.
The Maoist rebels, who claim inspiration from Chinese revolutionary leader Mao Zedong, have been fighting India's government for more than four decades, demanding land and jobs for tenant farmers and the poor. The rebels have thousands of fighters and are active in several parts of India.
They routinely attack government troops and officials and have been called India's greatest internal security threat.