According to the United States Census Bureau, Madisonville has a total area of 5.8 square miles (15 km2), all land.

As of the 2020 United States census, there were 5,132 people, 1,969 households, and 1,131 families residing in the city.

The City of Madisonville originally began as the town of Tellico, and prior to that a Cherokee village of the same name.

The Calhoun Treaty and resulting Hiwassee Purchase of 1819 opened the area for white settlement.

[12] Hiwassee College, now closed,[13] is located just north of the Madisonville city limits.

Madisonville is also home to a satellite campus of Cleveland State Community College.