He joined the Church of Jesus Christ of Latter Day Saints in the 1830s and later served as a missionary in Northumberland County, Pennsylvania.

For many years Woolley was bishop of the 13th Ward of the Church of Jesus Christ of Latter-day Saints in Salt Lake City.

Woolley, being a man of influence and wealth, was appointed to serve as the leader of the East Rochester branch of the church.

Woolley continued to prosper and soon was financing Mormon operations and loaning money to the founder of the church, Joseph Smith.

[4] When conflict between Mormons and non-Mormons reached a peak and Joseph Smith had been killed by an angry mob, the Illinois legislature asked the Mormons to leave Illinois in 1844 and in 1846 [3] Woolley and his family began the westward trek towards their new home in Utah, which at the time was still land claimed by the Republic of Mexico.

[5] Arriving in the Salt Lake Valley in 1848, the family was assigned a lot which was at the current location of 300 East and 300 South (now downtown).

Contrary to the anti-Mormon stereotypes of the nineteenth century, Brigham Young's bishops were not sycophants or lackeys.

In a painting commissioned by Brigham Young called "President Young and His Friends," Bishop Woolley is depicted along with Heber C. Kimball, Daniel H. Wells, George A. Smith, and four others.Woolley also served several terms as a representative in the Utah Territorial Legislature and as Salt Lake County Recorder.

In business, he assisted in the forming of the Deseret Telegraph Company and Zion's Cooperative Mercantile Institution (ZCMI).