The victim was identified as Wirat Bamrungwong, 43, Pol Col Chonnawee Chamareuk, superintendent of Nong Chik police station, said.
Pol Col Chonnawee led a combined force of police and soldiers to inspect and investigate the crime scene on a highway in the district.
A preliminary investigation found that Mr Wirat was shot once in his head by two assailants on a motorcycle armed with a pistol while he was riding the motorcycle to work at a lathe factory in the provincial seat.
The victim died immediately at the crime scene, Col Chonnawee reported.
Initially, police investigators presumed that the shooting was aimed at continuing the atmosphere of daily violence in the province.
The violence in the three southernmost border provinces of Pattani, Yala and Narathiwat have escalated since 2004 with bombings and shootings occurring on an almost daily basis. So far, the insurgency has claimed about 4,800 lives, including residents and government officials.