William Joseph Peele was born on 1855 January 31 near Jackson in Northampton County, North Carolina, the youngest of fourteen children of Isaac and Nancy Thompson Cobb Peele. His father was a prosperous farmer, slaveowner, and participant in county government. Financed by two brothers-in-law, Peele became a freshman at the University of North Carolina when it reopened in 1875 after being closed for five years following the Civil War. He studied classics and graduated in 1879. Peele then studied law, obtained his license, settled in Raleigh, and formed a partnership with Ernest Patrick Maynard, a Wake County native and fellow member of the University of North Carolina's class of 1879.

Peele believed his university education had not prepared him to earn a living and therefore became convinced that the state needed to develop industrial education. In May 1884 Peele helped establish the Watauga Club, which promoted various projects, including a statewide topographical survey, under his leadership. The Club's primary goal was the establishment of an industrial school in North Carolina for training manufacturers, mechanics, and farmers. Through the combined efforts of the Watauga Club and Leonidas Lafayette Polk's organized farmers, North Carolina College of Agriculture and Mechanic Arts, later North Carolina State University, was established in 1889. Between 1899 and 1901, Peele served on the board of trustees of the College, a position he held at the University of North Carolina between 1891 and 1897.

In 1897 Peele founded the North Carolina Publishing Society to print his . He was also the author of the (1892) and (1907). Additionally, Peele remained active in state and community endeavors. He was a member, 1900, of the Monday Evening Club of Raleigh. In 1901 he helped organize the State Literary and Historical Association and served as chairman of the committee to draft its constitution. Two years later Peele wrote the bill and obtained General Assembly support for the establishment of the North Carolina Historical Commission. The governor appointed him one of the Commission's first five members; Peele served as its first chairman and remained a member of the agency until his death on 1919 March 27. He was survived by his wife Elizabeth Bellamy Peele, a native of Raleigh whom he had married on 1909 September 4 after a twenty-one-year courtship.