Randa Duncan was born in 1962. Her Father, Dan Duncan, was the co-founder of Enterprise Products.
Williams is a member of the board of trustees for the Houston Zoo, was a member of the board of trustees for the Houston Museum of Natural Science since 1995 and its chairman. She was on the trustee boards for the Manned Space FLIGHT Education Foundation, River Oaks Baptist School and the Houston A+ Challenge.
In 2013, Williams was elected as Enterprise Production Partners' non-executive chairman.