Madisonville is a city in Monroe County, Tennessee, United States. The population was 3,939 at the 2000 census. It is the county seat of Monroe County and the location of Hiwassee College.
Madisonville is located at 35°31′11″N 84°21′49″W / 35.51972°N 84.36361°W / 35.51972; -84.36361 (35.520691, -84.362905). It is situated along U.S. Route 411 just east of its junction with State Route 68, near the center of Monroe County. The Unicoi Mountains rise prominently to the southeast.
According to the United States Census Bureau, Madisonville has a total area of 5.8 square miles (15.0 km²), all of it land.