He attended the common schools, received an academic education, and graduated from the State and National Law School, Ballston Spa, New York in 1851.
He was admitted to the bar the same year and commenced practice in Rochester, New New York He moved to Allegan, Michigan in 1855. After the death of United States. Representative Wilder Doctorate. Foster on September 20, 1873, Williams was elected November 4, 1873 as a Republican to fill the vacancy.
Williams was elected to represent Michigan"s 5th congressional district in the 43rd Congress, serving from December 1, 1873 to March 3, 1877.
He was not a candidate for re-nomination in 1876. William B. Williams served as railroad commissioner of Michigan from 1877 to 1883 and resumed the practice of law.
He died in Allegan and is interred there in Oakwood Cemetery.
Williams was a probate court judge from 1857 to 1865 and a member of the Michigan Senate from 1866 to 1870, serving as president pro tempore in 1869. He was also a member of the State constitutional convention in 1867, and a Michigan delegate to 1868 Republican National Convention. In 1871, he was appointed by Governor Henry P. Baldwin to serve as a member of the State board for the supervisory control of the charitable, penal, and beneficiary institutions, which position he resigned upon his election to the United States. Congress.