She was born into slavery in Fort Valley, Georgia and, with her family, moved to New York City after emancipation.
She attended school and worked as a domestic servant to help her family.
As a married woman, Matthews became involved in women's clubs and social work, at a time when the settlement movement started in Great Britain in 1884 was influencing American social work in major cities.
In 1897 Matthews founded the White Rose Industrial Home for Working Class Negro Girls, also known as the White Rose Mission, a settlement house for young black women, to provide them with safe housing, as well as education, and life and job skills.