This paper examines the role of proactive personality in the receipt of informal mentoring received (i.e., psychosocial and career-related mentoring) among a sample of 174 early career employees in China. The regression results indicated that networking behavior mediated the relationship between proactive personality and career-related mentoring, whereas voice behavior mediated the relationship between proactive personality and psychosocial mentoring. Furthermore, core self-evaluations moderated the aforementioned two indirect relationships such that they were stronger at higher levels of core self-evaluations. Our analyses also showed that the moderating effects occurred at the first stage of the indirect relationships. We discuss the theoretical and practical implications of these findings. Copyright © 2012 John Wiley & Sons, Ltd.