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Munby was born in York. He was educated at Trinity College, Cambridge, graduating with his BA in 1851, and was called to the Bar from Lincoln's Inn in 1855. He worked as a civil servant in the Ecclesiastical Commissioners' office from 1858 until his retirement in 1888. His published poetry included Benoni (1852) and Verses New and Old (1865). He taught Latin at the Working Men's College for more than a decade and helped promote the Working Men's College Volunteer Corps, a response to the national call for Volunteer Rifle Corps (1859) to combat a perceived threat from Napoleon the Third. Munby penned verses of support, the Invicta: a Song of 1860, for the 19th Middlesex Regiment, a regiment to which the W.M.C.V.C. was attached. In 1864, a sister Working Women's College was established; Munby was a leading spirit of, and teacher at, the new college.
Munby had a lifelong fascination with working-class women, particularly those who did hard physical labor. His favorite pastime was to wander the streets of London and other industrial cities, approach working women and ask them about their lives and the details of their work, while noting their clothes and dialects. These observations went into his journals. He was an amateur artist, and his diaries contain sketches of working women.
He also collected hundreds of photographs of female mine workers, kitchen maids, milkmaids, charwomen, acrobats and so on. These diaries and images provide historical information on the lives of working-class Victorian women. Much of his obsession is hinted at in his last book, Faithful Servants: being epitaphs and obituaries recording their names and services (1891). His papers are housed at Trinity College, Cambridge, there is a list of his papers on the Cambridge Janus website
In 1854, Munby was on one of his urban wanderings when he met Hannah Cullwick, a Shropshire-born maid-of-all-work. They formed a relationship in which Munby was the master and Cullwick the slave, with him training her in the virtues of hard work and loyalty. His scenarios also included elements of ageplay and infantilism, with Cullwick holding him in her lap or carrying him.
They had a secret marriage in 1873. However, Cullwick resisted his efforts to make her into a lady, and she lived with him as a domestic servant, not a wife. She would, however, play the role of a lady wife on their trips to Europe. They separated in 1877, but continued to see each other until Cullwick's death in 1909. The marriage remained a secret from all but a few close friends; he revealed it to his brother only a few months before his own death from pneumonia.
- Judith Flanders. Inside the Victorian Home: A Portrait of Domestic Life in Victorian England. New York: W. W. Norton, 2004.
- Diane Atkinson. Love and Dirt: The Marriage of Arthur Munby and Hannah Cullwick. New York: Macmillan, 2003.
- Barry Reay. Watching Hannah: Sexuality, Horror and Bodily De-formation in Victorian England. Reaktion, 2002. (ISBN 1-86189-119-9)
- Anne McClintock, Imperial Leather: Race, Gender, and Sex in the Colonial Contest. New York: Routledge, 1995. (ISBN 0-415-90890-6)
- Derek Hudson. Munby: Man of Two Worlds. Gambit, 1972. (ISBN 0-87645-066-4)
- Michael Hiley Victorian Working Women: Portraits from Life. Gordon Fraser, 1979 (ISBN 978-0-86092-033-5)