He enlisted in 1776 and fought in the American Revolutionary War as a regimental commissionary officer. He served in the Battle of Cowpens of January 17, 1781. In 1790, he was elected to the North Carolina House of Representatives.
On January 1, 1786, he married Nancy Glasgow (1771-1857), daughter of James Glasgow (1735-1819) who served as North Carolina Secretary of State from 1777 to 1798. They had six children. Their son Willoughby Williams, Jr. (1798-1882) went on to live in Woodlawn, a National Register of Historic Places-listed mansion in Nashville, with his wife m. Nancy Nichols (1808-1844).
- Zella Armstrong, Some Tennessee Heroes of the Revolution: Compiled from Pension Statements, Genealogical Publishing Com, 2009, p. 117 
- William Stevens Powell (ed.), Dictionary of North Carolina Biography, University of North Carolina Press, 1986, p. 304 
- Lineage Book, Daughters of the American Revolution, 1936, p. 269 
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