Williams is the author of four novels. Her first, State of Grace (1973), was nominated for a National Book Award for Fiction. Her most recent novel, The Quick and the Dead (2000), was a finalist for the Pulitzer Prize for Fiction. Her first collection of short stories was Taking Care, published in 1982. A second collection, Escapes, followed in 1990. A 2001 essay collection, Ill Nature: Rants and Reflections on Humanity and Other Animals, was a finalist for the National Book Critics Circle Award for Criticism. Honored Guest, a collection of short stories, was published in 2004. A 30th anniversary reprint of The Changeling was issued in 2008 with an introduction by the American novelist Rick Moody.

Her stories and essays are frequently anthologized, and she has received many awards and honors, including the Harold and Mildred Strauss Living Award from the American Academy of Arts and Letters and the Rea Award for the Short Story.

Williams was born in Chelmsford, Massachusetts. She received a BA from Marietta College and a MFA from the University of Iowa. She has taught creative writing at the University of Houston, the University of Florida, the University of Iowa, and the University of Arizona. For the 2008-2009 academic year, Williams is the eminent writer in residence at the University of Wyoming, where she teaches. She lives in Key West, Florida, and Tucson, Arizona. She was married for 34 years to L. Rust Hills, famous Esquire fiction editor, who died on August 12, 2008.

Williams's fiction often portrays life as a downward spiral, and the failure of life in America, from a spiritual as well as economic perspective, as a virtual certainty. Her characters, generally from the Middle Class, frequently fall from it, at times in bizarre fashion, in a form of cultural dispossession. Characters are usually divorced, children are abandoned, and their lives are consumed with fear, often irrational, such as the little girl in the story "The Excursion" who is terrified that birds will fly out of her toilet bowl.

Novels

• State of Grace (1973)
• The Changeling (1978)
• Breaking and Entering (1988)
• The Quick and the Dead (2000)

Story collections

• Taking Care (1982)
• Escapes (1990)
• Honored Guest (2004)

Nonfiction

• Ill Nature: Rants and Reflections on Humanity and Other Animals (essays) (2001)
• The Florida Keys: A History & Guide, illustrated by Robert Carawan (Tenth Edition) (2003)