James Williams was born in Prince George's County, Maryland, and moved with his family to Mechanicsburg, Champaign County, Ohio in 1831.
He was educated, studied medicine, and was admitted to practice in 1843.
[1] When Williams returned to Champaign County in 1851, he was elected to the Ohio House of Representatives for the 50th General Assembly in 1852–1853.
[2] In 1856, Williams went to the State Capitol in Columbus with Ohio State Auditor Francis M. Wright, and served for sixteen years as clerk, chief clerk and deputy in the office.
He was elected as State Auditor in 1871 and re-elected in 1875, serving eight years.