Soon after the establishment of the sisters in Los Angeles, it became evident that there was a third area where their services were sorely needed. This small community was Santa Barbara. Bishop Amat of Monterey (Santa Barbara) wrote to Emmitsburg and requested sisters for this part of his diocese. Emmitsburg responded and named Sisters Mary Mullane and Andrea Gibbs for Santa Barbara.

These two sisters and five others (destined for Los Angeles and San Francisco) boarded a steamer and sailed from New York to Panama on November 16, 1857. They arrived on the Atlantic side and crossed the Isthmus in rail cars. When they reached the Pacific side, they boarded another steamer and sailed on to San Francisco, where they arrived 31 days after their departure from New York. They waited several days and then boarded another smaller steamer and sailed on to Santa Barbara where they arrived on January 5, 1858. Sister Angelita Mombrado (from Los Angeles) joined them on January 8th.

Sister Mary Mullane was the leader of this colony of sisters in Santa Barbara. Here, they opened an English-speaking school and orphanage.

The Daughters of Charity have provided more than 150 years of continuing service to the people of Santa Barbara.