He graduated from Brown University in 1818, studied at the Litchfield Law School, and became an attorney in Lancaster, New Hampshire.
A Democrat, Williams served in the New Hampshire House of Representatives from 1830 to 1831, the New Hampshire State Senate from 1832 to 1834, and the New Hampshire House again from 1835 to 1836. In 1847 he was elected Governor, and he served two one-year terms, June 3, 1847 to June 7, 1849. After leaving the governorship, Williams was appointed Coos County Judge of Probate, and he served until 1852.
In 1853 he was appointed to the United States. Senate, temporarily filling the vacancy caused by Charles G. Atherton"s death, and he served from November 29, 1853 to August 4, 1854.
Williams died in Lancaster, New Hampshire on September 29, 1864, and is buried in Lancaster"s Summer Street Cemetery.
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