This study examined two value orientations (i.e., a doing orientation, or the tendency to commit to work ethic and goals, and a mastery orientation, or the tendency to seek control over outside forces) as mediators in the relationship between core self-evaluation and career decision self-efficacy. Data were collected from 802 Chinese university students and analyzed employing structural equation modeling. Results showed that both doing and mastery orientations fully mediated the relationship between core self-evaluation and career decision self-efficacy. Mastery orientation exhibited a stronger mediating effect on this relationship than did doing orientation. These findings reveal some important mechanisms underlying the role of core self-evaluation in career decision-making processes and offer useful implications for researchers and practitioners.