Charles Burgess Williams was born on 1871 December 23, in Shiloh, Camden County, North Carolina. He was the son of farmer Robert J. and Susan Burgess Williams. Williams' association with North Carolina State University began when he registered for classes on 1889 October 3, the day the North Carolina College of Agriculture and Mechanic Arts first opened its doors. A member of the College's first class, Williams was captain of the first football team. He graduated in 1893 with highest honors and a Bachelor of Science in agriculture.

Upon graduation in 1893, Williams was hired as the College's first instructor of chemistry and the assistant chemist of the North Carolina Agricultural Experiment Station. Williams served in the latter capacity until 1896, the same year he obtained a Master of Science in Agriculture from the College. For the academic year 1896-1897, Williams attended the Johns Hopkins University on a fellowship in chemistry. He returned to the College and resumed his position at the Experiment Station, remaining there until 1906. In 1906-1924 and 1926-1940, Williams served as the College's first head of the Department of Agronomy at the North Carolina Experiment Station. He was named Director of the Experiment Station in 1907 and served until 1912. He was Vice-Director from 1913 until 1940. He was the first Dean of the School of Agriculture between 1917 and 1924.

Williams' research focused on soybeans, soil surveys, and fertilizers. Between 1896 and 1934 he published more than 230 articles, bulletins, and books on these subjects. During his academic career, Williams studied at the National Graduate Summer School of Agriculture at Ohio State University (1902) and researched agriculture in California (1899), Ontario, Canada (1904), and Europe (1928). While at the College, Williams served as the Chairman of the North Carolina state soil survey (1915), Chairman of the Southeastern Tobacco Research Committee (1920-1941), and Chairman of the Southeastern Agronomy Research Committee (1927-1931 and 1936-1942). He was a member of Phi Kappa Phi, the National Grange, and a fellow in the American Association for the Advancement of Science. He was also a charter member of the American Society of Agronomy and its president in 1926. For his contributions to agricultural studies, Williams was listed in and was honored in 1941 by the Association of Southern Agricultural Workers.

Williams retired from administrative duties in 1940, but remained an active College faculty member until his death on 1947 June 25. Williams had served the institution for more than fifty-three years, longer than almost any other man until that time. He was survived by his wife Margaret Williams Moring Williams, one son, and two daughters. Margaret, a native of Raleigh, North Carolina, was born on 1879 October 4, and was a graduate of Peace College in Raleigh and the Southern Conservatory of Music in Durham, North Carolina. The couple married on 1900 July 5.