Williams-Paisley was born in Rye, New York, the daughter of Linda Barbara (née Payne), a fund-raiser, and Gurney Williams III,[citation needed] a health and science writer.

She left Northwestern University during her sophomore year to appear in the 1991 film version of Father of the Bride but returned to complete her degree in drama.

[3] She later appeared in Indian Summer (1993), Coldblooded (1995), The War at Home (1996), and in 1996 landed the lead role in the ABC drama series Relativity.

On stage, Williams-Paisley replaced Arija Bareikis as Sunny in The Last Night of Ballyhoo, written by Alfred Uhry (of Driving Miss Daisy fame) sometime later in the play's February 1997 to June 1998 run.

In 2012, Williams-Paisley began starring in the recurring role of Peggy Kenter in the ABC drama series Nashville.