A native of Washington, D.C., Williams' notable soap roles included stints on The Doctors as the first Dr. Maggie Fielding Powers and on The Edge of Night as television station owner Margo Huntington Dorn.
Her last soap opera role was as alcoholic June Slater on Loving, a role that, for a short time, reunited Williams and her former Search for Tomorrow co-star, John Cunningham (he had played Janet Bergman's psychiatrist husband Wade Collins).
Ann Williams died from cancer in 1985 in Bedford, New York. She was 50 years old.
Williams had four children with husband Robert Daniel Peter Welch, who died April 21, 1982): Amanda Gordon Welch (born 1965), Elizabeth Morgan Welch (born 1969), Daniel Merryman Welch (born 1971) and Diana Rebecca Welch (born 1977).
Almost all of the Welch children were minors at the time Williams died. The four siblings wrote a book about their family life after their parents' untimely deaths, The Kids Are All Right: A Memoir (Harmony/Random House, 2009).