Villiers was elected as a Liberal Member of Parliament for Wolverhampton in 1835. In 1837, 1838, 1839, 1840, 1841, 1842, 1843, 1844, 1845 he launched parliamentary debates in attempts to repeal the Corn Laws. In 1838, he spoke to over 5000 "working class men" in Manchester and told them that the presence of so large an audience gave him the proof that "the working class man was with him". Villiers was unsuccessful in his attempts, but in 1840 sat on the Committee on Import Duties that provided much of the evidence that pressured Robert Peel into his sliding scale concession in 1842. The bluebook produced by the Committee on Import Duties was published in pamphlet form and distributed across the country by the Anti Corn Law League, it was reprinted in America and quoted by all leading newspapers of the day, the Spectator published it in abridged form. In February 1842 Villiers was called by Monckton Milnes MP the "solitary Robinson Crusoe standing on the barren rock of Corn Law repeal". In 1842, the majority in favour of retaining the Corn Laws had been 303, at the vote on Villiers motion in June 1845 it was down to 132. After repeal in 1846, the press said of Villiers that he was "the most persevering and undaunted supporter of those principles within the house". David Ricardo, Chairman of the Free Traders in London wished to raise money to give to Villiers in recognition of his work, Villiers declined this.