When Oliver Cowdery and other early Latter Day Saints were traveling through Kirtland, they taught and baptized many in Rigdon's congregation, including Williams.

[3] On July 20, 1832, Williams was appointed scribe to Joseph Smith and joined the church's First Presidency the next year.

He was a member of the committee appointed to publish the Doctrine and Covenants, a portion of the church's canon, as well as the church's first hymnal from 1835, compiled by Smith's wife, Emma, under the auspices of F.G. Williams & Co.[3] In 1837, Williams was elected a justice of the peace in Kirtland, appointed an officer in the Kirtland Safety Society, released from the First Presidency, and moved to Far West, Caldwell, County, Missouri.

He was excommunicated in absentia in March 1839 by proceedings in Nauvoo, Illinois, while Joseph Smith was in Liberty Jail, Missouri.

[7] Williams was restored to fellowship at a church conference presided over by Smith in April 1840.