Beginning as a longhunter fort prior to its permanent settlement, the site of the town was part of a 600-acre tract of land bought by James Brigham in 1782. Ten years later, Brigham gave 30 acres to Sullivan County for use as a county seat and established a hotel nearby. The town was named Blountville after William Blount, the first governor of the Territory of the United States South of the River Ohio.
Blountville was a crossroads in the late 1700s, welcoming travelers headed west on the route beginning in Abingdon, Virginia and offering at least three different routes out of town. Blountville was a natural stop for stagecoaches to change drivers and horses. In only a few short years, Blountville became a major stopover on the Great Stage Road. If Blountville were incorporated, it would qualify as the second oldest municipality in Tennessee (second only to Jonesborough).