The land for the courthouse square was donated by Marcus Monroe (1793–1870), a local minister.

To defend the new county, its supporters retained the services of Horace Maynard (1814–1882), a Knoxville-area attorney and later U.S. Postmaster General.

After Maynard successfully defended the new county in litigation proceedings, Liberty was renamed "Maynardville" in his honor.

[17][18] Throughout the early to mid-20th century, State Route 33 through Maynardville was part of the infamous Thunder Road, which was used by bootleggers to illegally transport and trade moonshine.

Like most mountains in the Ridge-and-Valley Appalachians, these two ridges are long and narrow, and often fractured into smaller hills and knobs.

The Norris Lake impoundment of the Clinch River is located about 5 miles (8.0 km) north of Maynardville.

According to the United States Census Bureau, the city has a total area of 5.4 square miles (14 km2), all land.

As of the 2020 United States census, there were 2,456 people, 896 households, and 528 families residing in the city.

According to 2010 Census report published by the East Tennessee Development District in 2012, the top three industries employing residents of Maynardville were professional services, trade, and manufacturing.

[30] In the 2009 film Inglourious Basterds, the character of 1 SSF First Lieutenant Aldo Raine, portrayed by Brad Pitt, is said to be a moonshiner from Maynardville.