A population-based survey of Australian women diagnosed with early breast cancer examined the uptake and acceptability of a peer support program, the Breast Cancer Support Service (BCSS). We examined the characteristics and perceptions of women who did and did not use the BCSS. More than one-third (36%) had used the BCSS, most of whom first heard of it from hospital staff (36%) or clinicians (16%). Women perceived meeting someone else with similar experiences (53%) as the most beneficial aspect of the program and 89% said they would definitely recommend it to others. The findings suggest that uptake is related to provision of information about the BCSS. Peer support programs appear to be acceptable to both women who do and do not use the BCSS. To ensure that women can choose whether to participate in peer support programs requires strategies that encourage health professionals to provide comprehensive supportive care information.