Born in Llanpumsaint, Carmarthenshire, and having had only a basic education, Williams began working in a cotton warehouse in London and soon built up his own business.
In 1833 he became a member of the Common Council of the City of London, and in 1835 was elected MP for Coventry.
As a result of a speech made by Williams on 10 March 1846, a government inquiry into the state of education in Wales was launched, culminating in the 1847 Reports of the Commissioners of Inquiry into the State of Education in Wales.
[2] He is buried in Kensal Green Cemetery, London, in a grave north-east of the main chapel, alongside his parliamentary friend Joseph Hume.
A plaque is dedicated to him in the village school he founded in Llanpumsaint.