This study aims to examine the role of entrepreneurial intentions and motivations in the interplay between humane-oriented personal values and entrepreneurial behavior. Using data from 593 individuals in 2010 and 2019, we uncover how and when humane-oriented personal values (conservation and self-transcendence) lead to self-employment. Results suggest that entrepreneurial intentions function as a mechanism that triggers self-employment decisions for individuals with humane-oriented personal values and that this effect is stronger when they engage in opportunity-based entrepreneurship. Finally, we discuss the implications of these findings for the literature on personal values and the intention-action link.