Although a large volume of literature has documented the role of public service motivation (PSM) as altruistic work values, few studies directly examine PSM’s impact on job choice. Using longitudinal data, this article examines the factors that affect people’s career choices, specifically the extent to which individuals with different work values choose different sectors when considering job characteristics and person–job (P-J) fit. The analysis reveals that people are more likely to choose jobs in the private sector than jobs in the public or non-profit sector when they have opportunities to satisfy their altruistic work values through relational jobs. The findings speak to the importance of P-J fit when people choose their initial jobs. Contributions to existing literature and implications are discussed.