The literature has shown that social support enhances people’s health and quality of life. However, in the Korean context—where a strong negative stigma is attached to single parents—building a social support is a major challenge for single parents. To provide social support to single mothers in Korea, our study focuses on a one-to-one peer support program provided by a single-parents association in Korea that matches volunteer mentors to volunteer mentees. We conducted focus group interviews with 19 voluntary divorced or widowed single mothers who participated in the program and applied a theme-based analysis. The results reveal: 1) women’s motivations for program participation, 2) what activities occurred during the program, 3) self-reported experiences and outcomes, and 4) participants’ suggestions for improving the program. The study is the first to examine a one-to-one peer support program among single parents in Korea, and it provides organizations and groups that want to design, develop, and evaluate a one-to-one peer support program with the conceptual basis and specific examples to do so effectively.