Villiers joined in 1825 a debating club called "The Academics", where several of his college friends and John Stuart Mill discussed political and economic topics. A speech of his, aon colonisation, attracted the attention of the chancellor of the exchequer. Not long afterwards Villiers gave up government service to embark on politics. His chief source of income at that point was from the agencies for Berbice and Newfoundland. At the general election in June 1826 Villiers was returned to parliament for the borough of Hedon in Yorkshire, and sat for it until the dissolution in 1830. In 1830 and 1831 he sat respectively for Wootton Bassett and Bletchingley, and voted for the Reform Bill. Between 1825 and 1828, Villiers and Sir Robert Wilmot-Horton wrote, under the pseudonym 'Vindex', articles to the Star newspaper, in which they refuted the objections that others had made to the analysis of slavery made by Thomas Moody, Kt., the Parliamentary Commissioner on West Indian Slavery, and defended the character of Moody. Villiers travelled in Ireland in 1828, and set out his views in long letters to Taylor. A letter written by him in February 1829 was shown to Richard Lalor Sheil, who then brought about the suppression of the Catholic Association. He suggested in 1831 the formation of the commission that laid the foundation of the new poor law, and assisted in its preliminary inquiries. On 18 May 1831 he became Secretary to the Board of Control under Charles Grant. Later in the year Villiers and Taylor entered as students at Lincoln's Inn. On 22 August 1831 he made a long speech in the House of Commons on the Methuen treaty with Portugal. The committees on Indian affairs were organised by Villiers, with the assistance of Lord Althorp. The renewal of the charter to the East India Company at this time preoccupied him.
Family
Villiers and Charlotte Harte had two children: Rev. Charles Lawrence Villiers, Rector of Croft Parish in Yorkshire, and Gertrude Villiers, who in 1853 married Rev. William Frederick Bickmore. Rev. Villiers married Florence Mary Tyssen Amhurst and had issue, including a daughter named Gertrude Mary Amelia Villiers who in 1896 married Hon. Robert Grimston.
Death
At the time of his death Villiers was a candidate for the constituency of Penryn and Falmouth in Cornwall. After three months' suffering from an abscess in the head, he died on 3 December 1832 at Carclew, the seat of Sir Charles Lemon, near Penryn, where he was staying. A monument was placed to his memory in Mylor church.