The suspect, identified only by his surname Nie, allegedly killed the son, daughter, nephew and niece of a local villager Kuang Runhua in Hengshan County yesterday.
All four victims were teenagers with the youngest being just 13 years old, state-run Xinhua news agency reported.
He was arrested by the police today. The motive behind the murder, however, was not immediately established.
Nie is also suspected of killing another villager, a 31- year-old Yu while he was on the run, according to Hunan's provincial Department of Public Security.