Madisonville is a home rule-class city in and the county seat of Hopkins County, Kentucky, United States, located along Interstate 69 in the st…Madisonville is a home rule-class city in and the county seat of Hopkins County, Kentucky, United States, located along Interstate 69 in the state's Western Coal Fields region. The population was 19,591 at the 2010 census. Madisonville is a commercial center of the region and is home to Madisonville Community College.