Williams was active in civic affairs, serving on the board or advisory council of such organizations as Urban Day School, Inner City Council on Alcoholism, S.E. Wisconsin Health Systems Agency, Wisconsin Black Women's Network, Central City Bicycle Safety Program, Family Services of Milwaukee, and the Wisconsin Black Women's Assembly. In 1975, she became secretary of the Northside unit of the Democratic Party of Wisconsin, moving up to First Vice-President in 1977; and she served as a delegate to various state Democratic conventions and on committees for the state and congressional district units of the party. In 1975, she was also appointed to the Wisconsin StateEqual Rights Council, where she would serve until 1980. In 1980 she won the Democratic nomination in what was then the 17th Assembly district by a vote of 1291 to 762, unseating four-term incumbent Walter L. Ward, Jr.; and was unopposed in the general election. She was assigned to the standing committees on commerce and consumer affairs; on aging, women and minorities; on consumer and commercial credit; on education; and on small business and economic development. In May 2010, Williams announced she would not seek reelection. She was succeeded by Elizabeth M. Coggs.
School choice
Williams was the author of the United States' first school choice legislation, approving school choice in 1989, and expanding the program to include religious schools five years later. She lectured at institutions including Harvard, Yale, Marquette, Stanford, and Johns Hopkins universities. From 1990–97, she earned some $163,000 in honoraria and expenses, far more than any other legislator in Wisconsin. The legislation brought Williams national fame, but she began to disown both the choice program and its supporters. Williams later said Michael Joyce of the Lynde and Harry Bradley Foundation and other school choice proponents wanted to expand the program to middle-class families by ending the income limits and called it "a Catholic program". She accused choice and voucher proponents of exploiting black parents and children, saying "I haven't changed. The people around me have changed." "I don't agree with the way things are going at all", she said in an interview in 2011. "It's no longer the program that I supported at first."
Awards and honors
She received such awards as UW-Milwaukee Lifetime Achievement Award, UW-Milwaukee Alumni Association's Distinguished Alumnus, National Black Caucus of State Legislators President's Award for Distinguished Service, and she was named by The New York Times as one of "Thirteen Innovators Who Changed Education in the 20th Century".