In 1835 a party led by Governor James Stirling and John Septimus Roe surveyed a route joining King George Sound with York via Williams to encourage inland settlement.

[4] 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.

A heritage trail takes visitors past some of Williams's historic buildings, and nearby wildflower stands and dryandra forests are also attractions.

One unusual feature is the Jesse Martin museum, a 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.