After serving in the U.S. Army Air Force from 1943 to 1946, he entered Montana State College, earning a B.S. degree in 1951 and, the following year, an M.F.A. degree at California College of Arts and Crafts in Oakland. Returning to Montana in 1952, he established a pottery workshop in Helena. In 1953 while teaching a three-week summer course at Black Mountain College in North Carolina, Voulkos met innovative figures in the arts such as Josef Albers, Robert Rauschenberg, and John Cage, which significantly influenced the direction of his work.
In 1954 Voulkos became chairman of the new ceramics department at Otis Art Institute in Los Angeles. His pottery shop soon became the mecca for artists in the area, launching the Los Angeles clay movement, with Voulkos as its leader. Despite the accolades for his work, Voulkos began to feel constrained by the traditional forms of pottery. His Black Mountain connections led to his meeting Franz Kline and other abstract expressionist artists in New York. Absorbing their ideas, he sought to use clay as an expressive, sculptural medium and began to execute many works on a monumental scale.
In 1959 Voulkos became professor of design and sculpture at the University of California at Berkeley.