Rebati Nayak, involved in over a dozen serious cases including murder, was captured during a joint combing operation, they said.
A functionary of Sambalpur-Deogarh-Sundargarh Zonal committee of CPI (Maoist), Rebati is the wife of Maoist leader Bimba Bhoi of Tampersingha village in the district, police said.
She was involved in Naxal violence since 2003 and as many as 18 non-bailable warrants were pending against her in police stations in Sambalpur and Deogarh districts, they said, adding that besides western Odisha, she was also active in Maoist activities in Jharkhand.
Rebati would be produced before the local court shortly and efforts are now on to capture her husband, police said.