Daniel Harvey Hill, the second son of Confederate general Daniel Harvey Hill and Isabella Morrison, was born at Davidson, North Carolina, on 1859 January 15. In 1880, Hill graduated from Davidson College with a Bachelor of Arts degree; shortly thereafter, he began teaching as a professor of English at the Military and Agricultural College at Milledgeville, Georgia. During the nine years he taught at that institution, Hill married Pauline White of Milledgeville (1885) and received a Master of Arts degree from Davidson College (1886). He received a Doctor of Literature from Davidson in 1905 and a Doctor of Laws from the University of North Carolina in 1910.

Hill returned to North Carolina in 1889 when he was hired at the recently-established College of Agriculture and Mechanic Arts (now North Carolina State University). For almost twenty years, he served as professor of English and bookkeeping, faculty secretary, and treasurer. In 1905 he was elected Vice-President, a position he fulfilled while remaining professor of English. Three years later, Hill became the third president of the College. He held that position for eight years, resigning in 1916 to write a history of North Carolina troops during the Civil War entitled (1926).

Hill's lengthy academic career was coupled with an equally extensive literary career. His interest in North Carolina history manifested itself in his book about the state in the Civil War for the twelve-volume (1899). Collaborating with colleagues, he wrote the textbooks (1907) and (1903); a series of five schoolbooks collectively known as (1906); and (1920). Throughout the late nineteenth and early twentieth centuries, Hill served as editor of , a weekly newspaper that had been founded by his father.

Hill participated in numerous organizations, mostly those with a historical or literary focus, during his time at the College of Agriculture and Mechanic Arts. He was a member of the North Carolina Historical Commission, the North Carolina Society of the Sons of the Revolution, United Sons of Confederate Veterans, and the Southern Educational Association. He was the president of the North Carolina Teachers Assembly, the North Carolina Folklore Society, and the North Carolina Literary and Historical Association. Hill also served as chairman of the state council of defense during World War I.

Following his retirement, Hill remained in Raleigh until poor health compelled him to relocate to the western mountains of the state. He died on 1924 July 31 at Blowing Rock, North Carolina, and was survived by his wife and five children.