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The present research aims to explore the impact of mentoring relationship on college graduates’ job search behavior among Chinese undergraduate students by examining the mediator of job search intention and the moderator of job search self-efficacy. A two-wave survey study was conducted in China ( N = 594). Our findings show a positive indirect relation between mentoring and college graduates’ job search behaviors through job search intention. The graduates’ job search self-efficacy positively moderated the indirect relationship such that when job search self-efficacy was higher, the influence of mentoring on behavior via job search intention was stronger. These findings extend the literature by clarifying how and when mentoring facilitates graduates’ job search behaviors and provide practical implications for facilitating a smooth school-to-work transition in China. As the first study that empirically clarifies why (through job search intention) and when (job search self-efficacy) mentoring function is positively related to job search behavior among Chinese undergraduate students, the present study contributes to the existing mentoring and job search literature. Future research is encouraged to extend the findings by integrating theory of planned behavior (TPB) with self-regulation theory toward deepening current understanding of how and when mentoring can contribute to a student’s success in job search behavior.