The Bihar Police's Special Task Force has also arrested another person, but his identity was yet to be made public.
Sources said the CRPF officer, identified as Assistant Commandant Sanjay Kumar Yadav, was deployed in the 159th battalion of the force in Gaya.
A senior Bihar Police officer said they had been tracking the CRPF man for the past two to three months, after they intercepted phone calls of a naxalite operating in the state.
The officer said the CRPF man has been kept under custody at a location in Gaya and he may be arrested later and added that they have cell phone records of the suspect, which are incriminating evidence.
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The CRPF confirmed the incident and said it has launched an investigation into the case.
"The officer has been identified and we welcome the initiative of Bihar Police. We have launched a probe into this case and we will be more than happy to find the facts of this case as we are the force which has lost the maximum number of troops and won gallantry medals in Naxal operations," CRPF Inspector General (Operations) at its headquarter in Delhi Zulfikar Hasan told PTI.
Sources said the case has rattled the force and it has sent a team of its senior officers to take charge of the situation and talk to the accused officer.
The accused officer, who hails from Bihar, joined the paramilitary force in 2009.