Pada Gumisingu was caught from near Kumbikota in Rayagada district while he was returning to his village Gundriguda from a Maoist camp at Narayanpatna in adjoining Koraput district today.
Three detonators attached with a tiffin box were recovered from him, police said.
Gumisingu was an associate of Maoist leader Nikhil and involved in ultra activities in the district for the past seven years.
Another Maoist Raghu Nayak against whom eight non-bailable warrants were pending was arrested from Birikot in Gajapati district yesterday.
Nayak was allegedly involved in torching of several mobile towers at Raipanka and Birikot and burning of a bus at Raipanka in recent years, Superintendent of Police, Gajapati, C S Meena said.