Williams is named after the Williams River which flows nearby. The river was discovered by Captain Thomas Bannister in 1831 while leading the first overland expedition from what now is Perth and Albany and was first shown on an 1833 map. More than likely, the name honours King William, who reigned from June 1830 until June 1837.
No settlement occurred until after Lieutenant Henry Bunbury explored the region in 1836, despite his assessment that "on the Williams the land is generally very bad and the water brackish."
After the building of Albany Highway by convicts in the 1850s, Williams became an important stopover point for passengers and changing of horses and became the main centre in the district. The Williams Hotel was erected in 1871, and a Road Board (predecessor to the current Shire Council) first convened in 1877. The Williams Hotel continues to this day.
One unusual feature is the Jesse Martin museum, an historic village and memorabilia collection constructed by a local farmer on his own property from old shops and post offices on the verge of being demolished in country towns, as well as barns full of old cars and farm machinery. (the museum was not signed and unfortunately missed by Bustout)