The history of Pickett Chapel begins with the first Methodist congregation in Lebanon, which was white and organized in 1812. In 1827, the congregation financed the construction of a permanent meeting house on Market Street. While the architect or builder is unknown, the physical construction of the building was accomplished by enslaved African Americans, many of whom would also come to worship at the Chapel, albeit in bondage, with the white congregation. At this time, it is was known simply as "the Methodist Church."

Services continued at Pickett Chapel with white and black congregants until 1856, when the white congregation outgrew the Chapel and had a larger church built one block south on East Main Street.

Built in 1856, this Gothic Revival building was constructed by the founding congregation when they had outgrown Pickett Chapel. It was located one block south of Pickett Chapel on East Main Street.

Little is known about Pickett Chapel between 1856 and the end of the Civil War, but in 1866 the Chapel was sold to thirty freedmen for the sum of $1500. The new African American congregation christened the building Pickett Chapel Methodist Episcopal Church, after Calvin and James Pickett who were brothers, Methodist preachers, and members of the Board of Trustees in the Tennessee Conference of the Methodist Episcopal Church, and who helped arrange the purchase of the Chapel.

Signed July 20, 1866, this is the deed transferring ownership of the old church on Market Street from the Tennessee Conference of the Methodist Church to thirty freedmen who established an African American congregation that came to be known as Pickett Chapel Methodist Episcopal Church. Services were held at Pickett Chapel until 1973.

The African American congregation held services at Pickett Chapel for 107 years, until the congregation also outgrew the Chapel and had a larger church built approximately one-half mile to the east. Interestingly, both congregations still exist today – the white congregation as Lebanon First United Methodist Church, and the black congregation as Pickett-Rucker United Methodist Church – and Pickett Chapel sits at the exact geographic mid-point between both modern churches.

Shortly after the African American congregation left Pickett Chapel, it was purchased by local historians Richard and Virginia Lawlor, who had visions of establishing a Wilson County history museum. While the Lawlor’s dreams were never realized, they did succeed in having Pickett Chapel listed on the National Register of Historic Places in 1977. Beginning in the 1980s and continuing into the 1990s, the Chapel served as home to at least two community theater troupes, "The Chapel Playhouse" and "Sound & Light."

By the 2000s, Pickett Chapel was vacant, in a state of disrepair, and in desperate need of structural stabilization and restoration. In 2007, the Wilson County Black History Committee (WCBHC) purchased the Chapel and began restoration efforts with technical assistance from MTSU’s Center for Historic Preservation (CHP) and funding from the Tennessee Historical Commission, began restoration efforts.