[2] Her mother was born in Sherburne, a small community in Chenango County, New York,[3] and was a housewife who dedicated her life to raising her children, and participating in church activities.

[4] Her family was part of a privileged class since her father had built a solid real estate portfolio, and owned a profitable business.

[3] In a 1904 autobiographical article in the Independent, Barrier recalled of her Brockport youth that "...there could not have been a relationship more cordial, respectful and intimate than that of our family and the white people of this community.

"[5][6] Barrier and her siblings, Ella and George, attended the "primary department" or campus school of the old Brockport Collegiate Institute.

After graduation, Barrier went south to teach at a school for blacks in Hannibal, Missouri, where she encountered a level of racism she never experienced in Brockport.

She reported that she was "shattered" by the discrimination she encountered and this new awareness of racism targeted toward women of color ultimately led her to pursue a lifetime of activism.

[3] Disheartened by the racism she was experiencing, Barrier left the south to study piano at the New England Conservatory of Music in Boston, Massachusetts.

[4] After leaving the conservatory in Boston, Barrier went to the Washington, D.C., area to teach, joining the emerging education movement, which focused on freedmen and freedwomen.

However, she also experienced significant difficulties due to her race when she enrolled in the School of Fine Arts in Washington to study portrait painting.

Barrier Williams and her husband were among the founding members of the Prudence Crandall Study Club, an organization formed by Chicago's elite black American community.

Barrier Williams was director of the art and music department,[9] and she led the women's group alongside Mary Jones, who was a mentor and friend to her.

"[3] Although many white women's organizations did not embrace their black counterparts as equals, Barrier Williams made a place for herself in the Illinois Woman's Alliance (IWA), which provided a bridge between the women of the Prudence Crandall Study Club and the greater world of public activism, particularly within the labor movement.

[3] Barrier Williams utilized her alliance with the IWA to facilitate her entry into the white women's club movement.

[9] Barrier Williams achieved broader public recognition due to her efforts to gain representation of Black individuals at the Chicago Columbian Exposition of 1893.

Her address was followed by a discussion by Anna Julia Cooper and Fanny Jackson Coppin, as well as words of praise for all three women's speeches from Frederick Douglass.

Barrier Williams proclaimed a continuing belief in the ability of religion and faith to correct society's problems.