The Pennsylvania College for Women, a historic women’s college in Pittsburgh, established a program in social service in 1908, at a time when new vocations were opening for college-educated women. This program is the earliest example of a social work program based at a liberal arts college in the United States. Using archival materials, this research examines the formation and the early years of the program. Four elements proved to be foundational to the viability of the program: an elective curriculum, institutional financial stability, effective leadership, and the concurrent Pittsburgh Survey. The program met vocational needs from both the students and the local workforce. The mission, structure, content, student learning, and challenges of the program are assessed. It grew rapidly over the next several years, with some minor changes. The program enjoyed expanded partnerships with local charitable agencies, and social service became increasingly central to the curriculum, the student experience, and the ideology of the college as a whole. Many of the alumnae from the program’s early years continued on to professional positions, some developing prominent careers in social work.