Abstract This four-wave longitudinal study examined whether structured volunteering initiated in later life enhances psychological well-being among Hong Kong older adults through the Social Cognitive Theory serial mediation pathway: prosocial behaviour → resilience → self-efficacy → psychological well-being. A pooled analysis (N = 1,232) compared a large non-volunteering control group (n = 1,173) with 59 newly joined volunteers in a community programme. Using RI-CLPM, serial mediation, Latent Profile Analysis, and mixed ANOVAs, results showed significant Group × Time interactions, with the volunteering group exhibiting greater improvements in prosocial behaviour, resilience, self-efficacy, meaning in life, and well-being. Volunteering nearly doubled the proportion of older adults in the high-adaptation profile by T4. Structured volunteering offers a low-cost, culturally congruent intervention for successful ageing.