Elizabeth Villiers, the eldest of the eight children of Sir Edward Villiers, was regarded as ungainly with a bad complexion and a squint, certainly not a beauty. However, she had a good figure and a long white neck. In 1677, with her sisters Anne and Katherine, she accompanied the young Princess Mary, who had married the Prince of Orange, to Holland.

In 1679 when the Prince of Orange made his first advances she tried to discourage him. What the Prince of Orange found attractive in her was that she was witty, intelligent and an excellent talker. She was arrogant, not vain, had a sense of humour and her reserved manner hid a genuine warmth and generosity. However, rumours of their affair reached Paris that year, probably by 1680, Princess Mary became aware of their relationship.

In October 1685 the Prince of Orange dismissed Mrs. Trelawny from his Court. He had disliked her for many years because of her intrigues between the Prince and Elizabeth Villiers. However, Mrs. Trelawny was not the only one to tell tales as Mary's father, hoping to break up his daughter's marriage, had encouraged others to relay domestic gossip to him. However, through the meddling of Mary's father the affaire became public and Elizabeth was sent back to England. To stop rumours continuing there, Elizabeth's father then begged the Prince and Princess of Orange to allow her to return to Holland. Elizabeth was given permission to return but Princess Mary refused to receive her. Elizabeth then went to live with her sister Madame de Puissars. Bentinck, favourite of the Prince of Orange as well as Elizabeth's brother-in-law, forbade his wife to visit Elizabeth. In the meantime the affaire with the Prince continued and was to last for over fifteen years.

In 1688 Elizabeth's sister Anne Bentinck was dying and, because they had not been on speaking terms for several years, Elizabeth went to her sister's house, keeping herself in the background. However, Princess Mary called her over and Elizabeth and Anne made their peace. After William and Mary established themselves as King and Queen in England, Elizabeth returned to London where, for a while, she lived again with her sister, Madame de Puissars. Then she moved into lodgings close to Kensington Palace and soon resumed seeing the Prince of Orange, who was now King William III. As before, the affair was conducted discreetly. William III settled Irish properties, which had belonged to his father-in-law, on Elizabeth Villiers .

When William III lost his wife, he was devastated and, as soon as he decently could, he married off his mistress to one of his regimental commanders and thereafter ignored her. It was in November 1695 that Elizabeth married George Hamilton, fifth son of the Duke of Hamilton. He was handsome, dark-haired, had nothing much to say but, for a younger son, was extremely rich. He had distinguished himself in every one of William III's battles and had been severely wounded at Namur. In 1695 George Hamilton became Brigadier-General and Earl of Orkney in January 1696. Their marriage though frowned upon by several members of the Hamilton family, was a happy one producing three daughters. Elizabeth, Countess of Orkney, kept up her friendship with politicians; and even twenty years later her opinions were still valued by Government ministers. In 1727 at the Coronation of King George II, her appearance was described by Lady Mary Wortley Montagu: "She exposed behind a mixture of fat and wrinkles; and before, a very considerable protuberance which preceded her. Add to this the inimitable roll of her eyes, and her grey hair and 'tis impossible to imagine a more delightful spectacle."

In their house at Cliveden on 5 September 1724, Elizabeth and her husband entertained King George I and, on 30 July 1729, Queen Caroline. On 19 April 1733, Elizabeth died, and her husband on 29 January 1737.