Roopesh, a Maoist leader from Kerala, has been arrested along with his wife and four others in Tamil Nadu, Kerala Home Minister Ramesh Chennithala announced on Tuesday.
"The arrest of Roopesh will be enough to a large extent to put an end to Maoist activities in the state," he said in Thiruvanthapuram.
He said the arrests in Coimbatore district followed a joint operation by the police forces of the southern states.
Chennithala added that the Kerala Police would interrogate Roopesh and the others. All of them are now with the Tamil Nadu Police.
Roopesh and his accomplices, all members of the banned Communist Party of India-Maoist, are implicated in more than a dozen cases in southern India.
His aged mother-in-law told the media that her daughter and Roopesh had not visited the family since 2008.
"They never used to even call us as they knew police were tapping our phones," she said.
According to a tea shop owner in the area where they were picked up by police on Monday, the Maoists were sipping tea when they were caught.
"Roopesh began shouting slogans... Without any resistance all of them were led away," the vendor said.
However, Tamil Nadu Police said that the Maoist leaders were arrested Monday night.
Roopesh, his wife Shyna and three others were picked up from their hideout in Coimbatore, around 500 km from Chennai, said a police official, adding of the other three, two are from Tamil Nadu and one from Kerala.
The arrested were being questioned on different aspects including their local accomplices in Coimbatore.
Police have also seized several mobile phones and other items.