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Barbara was the only child of William, second Viscount Grandison (making her a cousin of the Duke of Buckingham) and the heiress Mary Bayning. In autumn 1643 Viscount Grandison died from a wound sustained in battle, leaving his widow and daughter in straightened circumstances.
Barbara was considered one of the most beautiful royalist women, but her lack of fortune left her with reduced marriage prospects. Her first serious romance was with the second Earl of Chesterfield, but he was on the lookout for a rich wife. On April 14, 1659 she married Roger Palmer, 1st Earl of Castlemaine (1634-1705) against his family's wishes; his father predicted that she would make him one of the most miserable men in the world. The two separated for good in 1662, following the birth of Charles. It is believed that Roger did not father a single one of Barbara's children.
Barbara became Charles's mistress in 1660, while Charles was still in exile. As a reward for her services, Charles made her husband Baron of Limerick and Earl of Castlemaine in 1661. Of her six children, five were acknowledged by Charles as his:
She had a bitter enemy in the Earl of Clarendon. Clarendon, one of the most powerful of the King's advisors, opposed her appointment as a Lady of the Bedchamber (as did, quite understandably, Catherine of Braganza, Charles's wife). By 1662 she had more influence in the court than did the Queen. This was followed by rumours of an estrangement between Barbara and Charles, as the result of his infatuation with Frances Stuart. In December 1663 Barbara announced her conversion to Catholicism, possibly in an attempt to consolidate her position with the King.
Barbara Villiers was famously extravagant. She was notorious for helping herself to money from the Privy Purse, as well as taking bribes from the Spanish and French. Her influence over the King waxed and waned. In June 1670 Charles created her Baroness Nonsuch, Countess of Southampton and Duchess of Cleveland. However, no-one in the court was sure whether this was an indication that she was being jettisoned by Charles, or whether this was a sign that she was even higher in his favours.
While the King had taken other mistresses, Barbara took other lovers, including the acrobat Jacob Hall and her second cousin John Churchill. Her lovers certainly benefited financially from the arrangement; Churchill purchased an annuity with £5,000 Barbara had given him. As the result of the 1673 Test Act which essentially banned all Catholics from holding office, Barbara lost her position as Lady of the Bedchamber.
In 1676 she travelled to Paris with her four youngest children.
In 1705 Roger Palmer died, and she married Major-General Robert Feilding whom she later prosecuted for bigamy. She died in 1709 after suffering dropsy.