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.