Police found six pistols, 12 rounds, and a motorcycle--collectively worth Rs 3,46,000--from them.
"The men were arrested following a tip-off that they are trying to sale firearms," said Superintendent of Police Megnathan Rajkumar.
Last night, police picked them up from a deserted road along the Nagpur-Tuljapur highway.
They were produced before a court which remanded them in police custody for three days.
They are identified as Salim Shah Suleman alias Salim Sagwan, a councillor, Ram alias Chimmanlal Sharma, Nilesh Sonore, Chandraprakash alias Tatu Ramakant Murab--all residents of Yavatmal--and Ravindra alias Ravi Ganesh Umale (35), a resident of Tunaki in Bhuldhana district.
"The accused have been booked under Arms Act and Mumbai Police Act," the SP told reporters.
At least three of the five accused have criminal past, he said.