Williams was born on a farm in Dulverton, Somerset, England, as the youngest of seven surviving sons of Amos Williams and Elizabeth Vickery. He was baptized into the Church of England. He came from several generations of farmers in Somerset, and attended Gloyn's in Tiverton, Devon until he was age 13, when he began working on his family farm. As a young man, he described himself as a "careless, thoughtless, godless, swearing young fellow". For unknown reasons, his family sent him to Bridgwater to be an apprentice at Henry William Holmes' draper shop. In 1837, Williams converted from Anglicanism to Congregationalism. He went to the Zion Congregational Church and became an involved member.
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In 1841, he went to London and worked as an apprentice at Hitchcock & Rogers, a draper's shop and became a member of the King's Weigh HouseCongregational Church, using his time for evangelization. After three years, in 1844, Williams was promoted to department manager. He married the owner George Hitchcock’s daughter, Helen Jane Maunder Hitchcock in 1853, and was taken into partnership at the drapers, renaming to George Hitchcock, Williams & Co. When Hitchcock died in 1863, Williams became the sole owner of the firm. Hitchcock and Williams had 7 children, his son Albert, a solicitor would go on to marry the granddaughter of Thomas Cook. Williams nephew John Williams married the only child of his lifelong London friend, Matthew Hodder, founder of British publisher Hodder & Stoughton. When George Hitchcock died in 1863, Williams became the sole owner of the firm. In 1868, Williams offered to contribute towards the election expenses of Charles Reed. When Williams died on 6 November 1905 at the Victoria and Albert Hotel, Torquay, England, he was president for societies including Band of Hope, London City Mission, Railway Mission and YWCA. His funeral took place at St Paul's Cathedral on 14 November 1905, with 2,600 people in attendance.
Appalled by the terrible conditions in London for young working men, on 6 June 1844 Williams gathered a group of 11 fellow drapers in the living quarters of Hitchcock & Rogers to create a place that would not tempt young men into sin. They were James Smith, Christopher. W Smith, Norton Smith, Edward Valentine, Edward Beaumont, M Glasson, William Creese, Francis John Crockett, E Rogers, John Harvey and John C Symons. The name, Young Men's Christian Association, was settled on at the suggestion of Christopher W Smith, a fellow draper at Hitchcock & Rogers. It promoted Muscular Christianity. One of the earliest converts and contributors to the new association was George's employer, George Hitchcock, who was the organizations first treasurer.
