Rossville was settled in April 1801 shortly after the U.S. Government initiated land sales west of the Great Miami River. Its original proprietors—John Sutherland, Henry Brown, Jacob Burnet, James Smith and William Ruffin—named the town in honor of Pennsylvania Senator James Ross (1762-1847), who favored Ohio statehood and advocated free navigation of inland rivers. These founders envisioned Rossville as a shipping port for the rapidly growing population of farmers settling west of the Great Miami. The most practical outlet for their products was by flatboat down the Great Miami, Ohio, and Mississippi rivers to New Orleans. The town of Rossville was founded in 1804, the year after the Louisiana Purchase, which made the Mississippi River a United States possession.
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The first Rossville post office opened in December 1819 in a store at the northwest corner of Main and B streets. From about 1805 ferries connected Rossville and Hamilton on the river's east bank. The first bridge, the privately built Miami Bridge, opened in 1819. This 380-foot "double-barrel" covered bridge, designed by James McBride, washed away in a flood in September 1866.
In the 1850 census Hamilton counted 3,210 inhabitants and Rossville 1,447. Voters in the two towns approved their union in April 1854, and the merger was completed in February 1855. In October 1975 the Rossville Historic District was placed on the National Register of Historic Places.