Libertyville is a city in Jefferson County, Iowa, United States. The population was 274 at the time of the 2020 census. It was platted in 1…Libertyville is a city in Jefferson County, Iowa, United States. The population was 274 at the time of the 2020 census. It was platted in 1845. According to the United States Census Bureau, the city has a total area of 0.49 square miles, all land.