© 2018, © 2018 Taylor & Francis. Research has found that public and nonprofit employees volunteer at a higher rate than their for-profit-sector counterparts, with the disparity typically explained as a behavioral consequence of their higher public service motivation (PSM). This article considers an alternative explanation that public and nonprofit jobs might offer greater formal avenues for participation, and hence that differences in volunteering might simply be an indicator of ease of access to such opportunities, rather than of inherent prosocial orientation. Examining whether individuals in different sectors use different pathways to access volunteer roles may improve our understanding of sectoral differences in prosocial behavior. This study accordingly examines how public, nonprofit, and for-profit private-sector employees access organizational volunteer roles. The results show a few significant differences in access to volunteer roles by occupation sector. The implications of these findings for voluntary management, corporate social responsibility research, and future research are discussed.