He was the son of Francis Napier, 8th lord Napier (1758-1823) and the father of Francis Napier, Lord Napier and Ettrick (1819-1898).
William John Napier served during the battle of Trafalgar (1805) as a midshipman. He later served as Lieutenant under Thomas Cochrane and Lord Dundonald.
A peer of Scotland, Napier was an elected Scottish representative in the House of Lords from 1824 to 1832.
In 1834, Lord Napier was appointed the first Chief Superintendent of Trade at Canton (now Guangzhou), in China. The Second and Third Superintendents were John Francis Davis and Sir George Best Robinson, respectively. Napier arrived at Macau in July 1834.
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