This study was designed to construct a model based on the concept of psychological well-being, in order to verify the relationship between Taiwanese elderly volunteering and their psychological well-being. Research data were collected via a questionnaire administered to the target population of this study, senior residents of Pingtung County aged 65 or more. The data were then tested and verified by confirmative factor analysis and structural equation modeling. The overall model showed higher levels of psychological well-being for the elderly who participated in volunteer work than those who did not, which again confirmed the positive relation between volunteer work and psychological well-being.