Background: Chronic pain is common among older adults and is associated with adverse physical and psychological outcomes. Given the burden of pain and limited healthcare resources, devising innovative and cost-effective ways of managing chronic pain is of high priority. The aim of this paper is to explore the experiences and perceptions of peer volunteers (PVs) in a peer-led pain management program among nursing home residents in Hong Kong. Methods: Forty-six PVs were recruited and trained to lead a pain management program (PAP). The PAP consisted of one 1 hour session per week for 12 weeks. It included 20 min of physical exercises performed under the supervision of PVs, followed by 30 min of pain management education, including information on pain situations, the impacts of pain, the use of drugs and non-drug strategies for pain management, demonstrations, and return demonstrations of various non-drug pain management techniques. Quantitative data were collected from questionnaires (demographics, pain situation, and pain knowledge) for all PVs. Qualitative data (PVs’ experiences in leading the PAP, their perceived benefits, barriers encountered, and recommendations for improving the PAP) were collected at week 12 (upon completion of the PAP). Data were analyzed using the Statistical Package for Social Sciences and content analysis for qualitative data. Results: A total of 46 PVs were recruited (34 females, 74%), with a mean ± SD age of 61.0 ± 5.1 years. Thirty-one of them reported having chronic pain. Before the training, their self-rated pain knowledge was 40.0 ± 20.5 (maximum 100 points) while their actual pain knowledge score was 86.1 ± 10.6 (maximum 100 points). The PVs reported an improvement in their knowledge and skills after leading PAPs. No PVs reported having received any negative comments about their role in leading the PAP but mentioned that they had received feedback on how to improve the program. Conclusions: This study provides further evidence that peer-led pain management programs are feasible and can lead to positive experiences for the PVs. Peer support models are coming into wide use because they show promise in helping patients to manage chronic conditions. Peer volunteers will become important resources in elderly care. The barriers that were identified may lead to improvements in the design and planning of future PAPs.