Williams was educated at Eton College and started his career as a schoolmaster at Ipswich School. On the outbreak of the Crimean War he joined the Royal South Lincoln Militia and fought at Sevastopol. He later went onto the stage and was called to the bar in 1862. In 1879 he was appointed junior Treasury counsel, retiring from the post in 1886 due to a growth on the larynx which seriously affected his voice, being succeeded by Sir Charles Willie Mathews, 1st Baronet. Williams took up a post as metropolitan stipendiary magistrate in 1886 and was appointed Queen's Counsel in 1888.
His clients included Catherine Wilson, whom he defended twice on murder charges; George Henry Lamson, hanged in 1882 for poisoning his brother-in-law; Percy Lefroy Mapleton, the "railway murderer", hanged in 1881; John Young, acquitted of manslaughter after his opponent in a boxing match died, establishing a legal precedent.
- Leaves of a life, 2 vols, 1890
- Later leaves (Macmillan) 1891
- "The case of the late Mr Montague Williams". British Medical Journal: 1440. 31 December 1892.
- Horace Bleackley (1929). The hangmen of England: how they hanged and whom they hanged : the life story of "Jack Ketch" through two centuries. Taylor & Francis. p. 245. ISBN 0-7158-1184-3.
- Thomas A. Green; Joseph R. Svinth, eds. (2010). Martial Arts of the World: An Encyclopedia of History and Innovation. ABC-CLIO. p. 465. ISBN 1-59884-243-9.
- Hugh H. L. Bellot (2005). The Inner And Middle Temple: Legal, Literary And Historic Associations (reprint ed.). Kessinger Publishing. pp. 85–87. ISBN 1-4179-5438-8.
- John Andrew Hamilton. "Williams, Montagu Stephen". Dictionary of National Biography, 1885-1900 61.
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