The people most in need in Sydney, in 1857, in the eyes of Archbishop Polding, were the destitute women of Sydney. With the aim of relieving their suffering he gathered together five women and formed a new religious congregation which he named the Sisters of the Good Samaritan of the Order of St Benedict. Their specific ministries were the care of needy women and the education of children, although Polding also wanted them to engage in general works of charity.

The Sisters began working in a women's refuge in Carters' Barracks, an old building once used as a prison in Pitt Street, Sydney. They visited the sick and the poor and looked after orphans, initially at Parramatta, then at Manly and finally at Narellan from 1910. The work begun at the refuge in Pitt Street was continued at St Magdalene's Retreat, Tempe, in Sydney, where the Sisters looked after girls committed to their care by the courts. Opened in 1887, Tempe closed almost 100 years later in 1983.

Education was always a major area of activity for the Sisters of the Good Samaritan. The first school was set up in Sussex Street in the heart of Sydney in 1861. Later other schools were established in NSW and throughout Australia. Now, there are ten incorporated college across Australia, and one in Japan.