Kewal Atkamwar, a former Zilla Parishad member in the district was attacked on Friday night when he was sitting with a friend in front of his brother's shop at main square in Etapalli taluka, they said.
The Maoists pumped five bullets from almost close range and fled from the scene.
Two others -- Prashant Kukulwar and Laxminarayan Parvatlawar -- who were sitting along with the deceased, sustained bullet injuries and were rushed to Gadchiroli civil hospital for treatment. Parvatalawar was later referred to Chandrapur civil hospital, the police added.
Atkamwar was the vice-president of Gadchiroli unit of NCP and was a close aide of former minister and tribal NCP leader Dharamrao Baba Atram.
This is the second political killing within three months. Naxals had earlier killed one Bahadur Shah Alam, president of Bhamragarh Taluka Congress Committee.
Maharashtra Home Minister R R Patil who is now the guardian minister of the Naxal affected district is also from the NCP.