Bedford Brown was born in what now is Locust Hill Township, Caswell County, North Carolina. His parents were Jethro Brown and Lucy Williamson Brown. After attending the University of North Carolina for one year, Brown was elected to the North Carolina House of Commons. In 1828, upon the death of Bartlett Yancey, Jr., Brown was chosen in a special election to replace Yancey in the North Carolina Senate. As was Bartlett Yancey, Jr., before him, Brown was elected Speaker of the North Carolina Senate. In 1829, he was elected to succeed John Branch as a United States Senator from North Carolina.

Leading up to the Civil War, Brown counselled in favor of North Carolina's remaining in the Union. However, after President Lincoln requested troops from North Carolina to serve in the Union Army, Brown along with most of his colleagues voted for secession.

In 1868 Brown, a Democrat, was again elected to the North Carolina Senate. However, the Reconstruction Republicans controlled the North Carolina Legislature and refused to seat Brown. He was replaced by Republican John W. Stephens. For more on John W. Stephens, including his murder in Yanceyville, North Carolina, by the Ku Klux Klan and the resulting Kirk-Holden War, to the Caswell County Historical Association.

On July 13, 1816, Brown married Mary Lumpkin Glenn. They had seven children: William Livingston, Bedford, Jr., Wilson Glenn, Isabella Virginia, Laura, and Rosalie. Brown was buried on the grounds at Rose Hill just outside Yanceyville, North Carolina.