Madisonville is the county seat of Monroe County, Tennessee, United States. It is located in East Tennessee on the eastern border of the st…Madisonville is the county seat of Monroe County, Tennessee, United States. It is located in East Tennessee on the eastern border of the state. As of the 2020 census, the city's population was 5,132. Madisonville 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.
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