Waterville is a city in Paint Creek Township, Allamakee County, Iowa, United States. The population was 109 at the time of the 2020 censu…Waterville is a city in Paint Creek Township, Allamakee County, Iowa, United States. The population was 109 at the time of the 2020 census. The first settlement in the neighborhood of what would become Waterville was in 1850. In 1854, Nathaniel Beebe erected the Waterville Mill. In 1855, Col. J. Spooner opened a store, and in 1856, James Beebe built a hotel. The Waterville Post Office was established in 1855. The Waukon and Mississippi Railroad was completed through town in 1877, at which point Waterville became the only station between Waukon and Waukon Junction.