This area was opened to European settlement following the Battle of Fallen Timbers in 1794, which took place about 26 miles to the east.

The Miami and Erie Canal was finished in 1843, bringing German immigrants to the area.

At the time, most employment existed through businesses which made products for farmers in the surrounding countryside.

[7] Four buildings in Napoleon are listed on the National Register of Historic Places: the county courthouse, the sheriff's house and jail, First Presbyterian Church, and St. Augustine's Catholic Church.

30.6% of all households were made up of individuals, and 14.5% had someone living alone who was 65 years of age or older.

30.9% of all households were made up of individuals, and 13.4% had someone living alone who was 65 years of age or older.

A major employer is the world's largest Campbell's Soup Company plant,[18][19] located on the southeastern end of the city; also Tenneco owns one of their largest Elastomer Plants there.

[20] Clear Channel Communications owns the local radio station licensed to Napoleon, WNDH 103.1 FM "The One",[21] which features a classic hits music format.