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He was elected as a Liberal MP in 1906.
In 1909 he published his best known book The Condition of England, in a survey of contemporary society with particular focus on the state of the working class.
In 1914 he was appointed to the Cabinet as Chancellor of the Duchy of Lancaster. However under the law at the time, any MP accepting an "office of profit under the Crown" was legally required to recontest their seat in a by-election. Masterman lost his own seat, though this was not uncommon, and stood in two further seats, losing each time. He resigned from the Government as a result. Many believed that a promising political career had been destroyed by the legal requirement, a hangover from the era when Parliament had sought to curb the influence of the Crown on MPs, which would be amended and finally repealed altogether in the next twelve years.
He served as head of the British War Propaganda Bureau (WPB) during the First World War. In this role, he recruited writers such as John Buchan and Arthur Conan Doyle to support the war effort.
Masterman eventually returned to the House of Commons in the 1923 general election but by this point the Liberal Party was in decline and, like most other Liberals, he lost his seat in the 1924 general election.
He married Lucy Blanche Lyttelton (1884 - 1977), a poet and writer, in 1908. Her biography of him was published in 1939.
| Preceded by: Charles Edward Henry Hobhouse | Chancellor of the Duchy of Lancaster 1914–1915 | Followed by: Edwin Samuel Montagu |