Participation in volunteer services can be regarded as an indicator of quality of life among adolescents. The Volunteer Functions Inventory (VFI) has long been used to assess the underlying motives of volunteers. Owing to conceptual, methodological and empirical limitations, the VFI could not be fully endorsed to understand Chinese adolescent volunteerism. Another scale was devised, called the Revised Personal Functions of the Volunteerism Scale (R-PFVS). This study focused on the exploration of the factorial structure of the R-PFVS. The R-PFVS was administered to a large sample of Chinese adolescents (N = 5, 946). Data were split into two halves: one for exploratory factor analysis and the other for confirmatory factor analysis. The scale showed good factorial validity. Seven factors were revealed, namely, well-being, learning, socializing, pro-social competence, altruistic concern, future plan, and civic responsibility functions. The factors were highly correlated with each other. A second-order factor model was established, and all seven factors were loaded on this higher-order abstract factor. The R-PFVS subscales and the overall scale demonstrated good internal consistency. The findings were compared with the VFI. The R-PFVS can be used in assessing the underlying motives behind volunteerism among Chinese adolescents and in studies on the quality of life.