William B. Hughes was born around 1838 in South Carolina to John and Martha Hughes. His father was a planter who owned $33,000 of real estate and $41,000 of personal property by 1860. Hughes grew up and attended school in Edgefield District, South Carolina, and by 1860, he was working as a farmer.
He served in the Edgefield Reserves during the Civil War, and in December 1861, the company “volunteered their services to the Governor of the State and the President of the Confederate States, for the special defense of South Carolina during the term of twelve months.” He mustered in as a private in Company A of the 22nd South Carolina Infantry. He was mortally wounded in the Battle of South Mountain on September 14, 1862, and his comrades reportedly “left [him] on the field.”