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Born into an ancient Welsh family, Williams-Wynn was the second son of Sir Watkin Williams-Wynn, 4th Baronet, by his second wife Charlotte Grenville, daughter of Prime Minister George Grenville.
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Williams-Wynn was educated privately, at Westminster School and Christ Church, Oxford.He was called to the Bar, Lincoln\'s Inn, in 1798.
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Williams-Wynn was an active member of parliament and considered an authority on the procedure of the House of Commons.This led him to be nominated for the post of Speaker of the House of Commons in 1817.However, he was defeated by Charles Manners-Sutton.During the late 1810's Williams-Wynn was leader of a group of MP's that tried to establish a third part in the House of Commons, acting on behalf of his cousin Lord Buckingham.However, the third party never materialized and the group instead joined the Tories.
In January 1822 Williams-Wynn was admitted to the Privy Council and appointed President of the Board of Control, with a seat in the cabinet, in the Tory government of the Earl of Liverpool.He remained in this post also in the administrations of George Canning and Lord Goderich.However, when the Duke of Wellington became Prime Minister in 1828, Williams-Wynn was not offered a position in the government.
This drove him into opposition, and when the Whigs came to power in November 1830 under Lord Grey, Williams-Wynn was appointed Secretary at War, although without a seat in the cabinet.He only remained in this post until April the following year,