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Born in Charlotte County, Virginia, Bouldin attended the common schools, then studied law. He was admitted to the bar April 12, 1813, and began to practice at Charlotte Court House, Virginia. He served as member of state house of delegates from 1825 to 1826.
Bouldin was elected as a Jacksonian to the Twenty-third Congress to fill the vacancy caused by the death of his brother Thomas Bouldin. He was reelected to the Twenty-fourth Congress, then as a Democrat to the Twenty-fifth Congress. He served in Congress from March 15, 1834, to March 3, 1839. He served as chairman of the Committee on District of Columbia (Twenty-fifth Congress). He resumed the practice of law and also engaged in agricultural pursuits. He died at his country home, "Forest Hill," Charlotte County, Virginia, March 30, 1854. He was interred in the private burial ground on his estate.