William T. Walters was born in Liverpool , Pennsylvania, near the Juniata River, on May 23, 1819. He arrived in Baltimore from Pennsylvania in 1840 and opened a wholesale liquor business. After acquiring a residence at 5 West Mount Vernon Place in 1857, he began to patronize American artists, both locally and in New York, and he also made his first purchases of works by contemporary European artists.

In 1862, Walters, a supporter of states' rights, departed for Paris with his wife Ellen (1822-1862) and their children Henry (1846-1931) and Jennie (1853-1922). Upon their arrival in Europe they were met by a fellow Baltimorean, artist George A. Lucas (1824-1909), who served as their advisor as they visited museums and artists' studios to buy works of art. At the 1862 International Exhibition in London, Walters developed an interest in Chinese and Japanese art, and he gradually formed an outstanding collection of ceramics, lacquers, and metalwork.

Returning to Baltimore in 1865, Walters was elected vice-president of the Safe Deposit and Trust Co. and played a pivotal role in refinancing the railroads in the Carolinas, which eventually merged to form the Atlantic Coast Line Railroad. He continued to expand his art holdings, forming an exceptionally rich collection of Barbizon and Academic masters. His reputation as a connoisseur was such that in 1873 he traveled to Europe as honorary U.S. commissioner to the Vienna World's Fair and as the first chairman of the acquisitions committee of the Corcoran Gallery of Art, Washington, DC. Walters opened his own private galleries at 5 West Mount Vernon Place to the public every spring, charging a 50-cent fee that went to charity. The most notable of the catalogues that he issued was Stephen W. Bushell's lavishly illustrated Oriental Ceramic Art.

Walters died in Baltimore in 1894, leaving his collections to his son Henry, who provided for the establishment of the museum that bears the family name today.

Johnston, William R. William and Henry Walters: The Reticent Collectors. Baltimore: Johns Hopkins University Press, 1999.