Williams was born in Oxford, England and educated at Hurstpierpoint College and Lincoln College, Oxford, where he graduated BA in 1854, and MA in 1860. He was ordained deacon in 1852 and priest in 1853 in the Diocese of Rochester.
He came to South Australia in 1861 without fanfare to take a position with St Peter's College as third master; in 1873 he was appointed second master, and subsequently bursar.
At the end of 1881, after allegations of Ritualism and subsequent divisions in the College Council, W. Bedell Stanford, who had been appointed Head Master by Bishop Short in 1879, resigned. Williams was persuaded to postpone his planned holiday to England, and was made acting Head, and in 1882 was formally appointed to the position. In April 1886 Williams and a College man-servant suffered from a severe attack of typhoid fever, but no student or other staff member was affected. In December that year he took twelve months' holiday to England, James Henry Lindon (8 June 1856 - 6 June 1897), later founder of Queen's College, North Adelaide, acting in his place.
In 1889 he resigned as Head Master, and was succeeded (briefly) by the Rev. Philip Edwin Raynor, M.A. ( - October 1930), who was in turn replaced by the Rev. Henry Girdlestone, M.A. (c. 1863 - 29 June 1926), perhaps the College's most successful headmaster.
In 1892 Williams was appointed Bishop's Chaplain to Dr. Kennion, then Dr. Harmer's Chaplain.
Williams was appointed to St. Peter's College' Board of Governors, a position he actively maintained until his death.
He collapsed and died aboard a tramcar while returning to his home "Woodspring" in Unley Park from St Peter's Cathedral, where he had been acting as chaplain at the morning church service. His remains were interred at the North Road Cemetery.
Williams married Celia Roubel Laurie (1 May 1852 - 16 March 1922) on 29 June 1871, Celia was a daughter of B. F. Laurie, SM., of "Southcott", Port Elliot.