Duff was the son of Alexander Duff, 3rd Earl Fife and Mary Skene.
On 9 September 1799, he married Lady Maria Caroline Manners (d. 1805), daughter of John Manners and Louisa Tollemache, 7th Countess of Dysart, but the couple had no children.
He volunteered to help the Spaniards against Napoleon, and fought at the Battle of Talavera as a major-general in the Spanish service.
He was Member of Parliament for Banffshire from 1818 to 1827. In 1827 he inherited Skene House in Aberdeenshire from his mother's family.
He was appointed a Knight of the Thistle and created Baron Fife in the Peerage of Great Britain in 1827. This title became extinct on his death.
He was Lord Lieutenant of Banffshire from 1813–1856.
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