She was married to James Scott, 1st Duke of Monmouth, and the couple had six children, only two of whom survived past infancy.

[4] Upon her marriage in 1663, her husband took her surname, and the titles of Duke of Monmouth, Lord Scott of Whitchester and Eskdaill, Earl of Dalkeith, and Duke of Buccleuch were created, with remainder to the heirs male of his body by Anne, failing whom to the heirs whomsoever of her body who shall succeed to the estates and Earldom of Buccleuch.

"[5] Following the Duke of Monmouth's death in 1685, the Duchess, whose titles were not affected by her husband's attainder because of the novodamus of 1666, resigned them into the hands of the Crown for a second time and obtained a new grant by a charter under the Great Seal, on 17 November 1687, of the title of Duchess of Buccleuch and her other honours to herself for life, and after her death to James, Earl of Dalkeith, and his heirs-male.

[6] James had been born in Rotterdam during the Second English Civil War, where his father was with his sister, Mary and his brother-in-law William II, Prince of Orange.

[7] The couple had six children:[5] Her husband, the Duke of Monmouth and Buccleuch, was attained and executed for high treason on 15 July 1685 following the failure of Monmouth's Rebellion, in which he had attempted to seize the English throne and overthrow James II (the younger brother of his father, who became King of England, Scotland, and Ireland in February 1685 following the death of Charles II).