This study uses role theory to examine the association between postretirement work and volunteering among retirees and to determine whether this association varies across poverty status. Data came from the 2012 wave of the Health and Retirement Study (HRS). The sample was restricted to respondents of older retirees (N = 6,619). We found that postretirement work positively influenced volunteering. However, poverty can be a risk factor of volunteering among older retirees. The positive effect of post-retirement work was found to be more significant in the near-poverty group. We provide an empirical foundation to help inform volunteer programs for retirees.