Coming under the influence of Charles Kingsley's father, then vicar of St Luke's Church, she devoted herself at the age of sixteen to parochial work in Chelsea.
In succession to Mary Howitt, she soon became secretary of the Langham Place Group which promoted the Married Women's Property bill, which was brought forward by Sir Thomas Erskine Perry in 1856 but was not fully passed till 1882.
In 1859, she undertook a private law-stationer's business at 12 Portugal Street, Lincoln's Inn, in order to give employment to middle-class girls.
[4] At the same time, she helped to establish the Victoria Press in association with her business in 1860 (under the charge of Emily Faithfull), and the employment bureau and telegraph school in Great Coram Street, with Isa Craig as secretary.
Even in the more settled Canterbury region, Rye realized the scheme was not going to work since the local populace emphasized their need for domestic servants or marriageable farmhands.
After visiting in New York the Little Wanderers' Home for the training of derelict children for emigrant life which Mr. Van Meter, a Baptist minister from Ohio, had founded, she resolved to give the system a trial in London.
Encouraged by Anthony Ashley-Cooper, 7th Earl of Shaftesbury and The Times newspaper and with the financial support of William Rathbone VI, M.P., in 1869 she purchased Avenue House, High Street, Peckham, and with her two younger sisters, in spite of public opposition and prejudice, took there from the streets or the workhouses waifs and strays from the ages of three to sixteen.
Fifty girls from Kirkdale industrial school, Liverpool, were soon put under her care; they were trained in domestic economy and went through courses of general and religious instruction.
To this house Miss Rye drafted the children from Peckham, and after further training they were distributed in Canada as domestic servants among respectable families.
Poor law children were subsequently received at Peckham from St. George's, Hanover Square, Wolverhampton, Bristol, Reading, and other towns.
Lord Shaftesbury remained a consistent supporter, and in 1884 Henry Petty-Fitzmaurice, 5th Marquess of Lansdowne, then governor general of Canada, warmly commended the results of her pioneer system, which Thomas John Barnardo and others subsequently adopted and extended.