Born in Deptford, then in Kent, James's parents died when she was young, and she was brought up by a former employee of her father.
She found work making confectionery, and in 1889 she joined the Women's Trade Union Association (WTUA).
Its activist Amie Hicks provided her with accommodation and legally adopted James as her daughter.
[1] The WTUA was refounded in 1894 as the Women's Industrial Council (WIC), and James remained active within it, serving on both its investigation and organisation committees.
Once she had completed this, James set up a series of "Working Girls' Clubs", providing lectures, physical drills, social meetings and citizenship classes.