Olivia Davidson, the daughter of a slave, was born in Mercer County, Virginia, on 11th June, 1854. The family moved to Ironton, Ohio, where Olivia attended the local high school. Eventually she moved to Memphis with her brother Joseph and her sister Margaret.

Olivia became a teacher in Memphis but was soon on her own after the death of her sister and the killing of her brother by the Ku Klux Klan. In 1878 Olivia moved back to Ohio where she enrolled at the Hampton Institute where she met a fellow student, Booker T. Washington. In 1881 Olivia helped Washington establish the Tuskegee Institute.

In 1884 Washington's first wife, Fannie Smith, died, and two years later he married Olivia. Olivia was a strong supporter of women's rights and in 1886 gave a talk to the Alabama State Teachers' Association on How Shall We Make the Women of Our Race Stronger?

Olivia Davidson Washington had two children, but her health was never very good and she died of tuberculosis of the larynx on 9th May, 1889.