Born near Churchville, Maryland, Webster received a classical training, and attended the Churchville Academy and later the New London Academy of Chester County, Pennsylvania. He graduated from Dickinson College of Carlisle, Pennsylvania in 1847, and afterwards taught school and studied law. He was admitted to the bar in 1851, and commenced practice in Bel Air, Maryland.

Webster became a member of the Maryland State Senate, serving from 1855 until 1859. During the American Civil War, Webster was colonel of the 7th Regiment Maryland Volunteer Infantry, serving in 1862 and 1863. He was elected as a candidate of the American Party to the Thirty-sixth Congress, as a Unionist to the Thirty-seventh Congress and as an Unconditional Unionist to the Thirty-eighth and Thirty-ninth Congresses.

Webster served in Congress from March 4, 1859 until his resignation in July of 1865, at which time he was appointed collector of customs at the port of Baltimore, Maryland, serving in that position from July 27, 1865 to April 15, 1869. Afterwards, he resumed the practice of his profession in Bel Air until he was again appointed collector of customs by President Chester A. Arthur on February 17, 1882. He served as collector until February 23, 1886. In 1882, he engaged in banking, which he followed until his death in Bel Air in 1893. He is interred in Calvary Cemetery, near Churchville.

This article incorporates facts obtained from the public domain Biographical Directory of the United States Congress.