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On November 2, 1848, he married Isabella Morrison, who was the daughter of Robert Hall Morrison, a Presbyterian minister and the first president of Davidson College, and through her mother, a niece of North Carolina Governor William Alexander Graham. They would have nine children in all. One son, Daniel Harvey Hill Jr., would serve as president of North Carolina State College (now North Carolina State University). Their youngest son, Joseph Morrison, would preside as the Chief Justice of the Arkansas Supreme Court from 1904 to 1909.