This study investigated mentoring relationships between doctoral students and faculty members. We examined initiation of mentoring as a mediator between key personality facets and mentoring received among 162 doctoral students (females = 77%, 77% psychology programs). Results confirmed that initiation of mentoring relationships by doctoral students significantly predicted mentoring received. Furthermore, mentoring initiation also mediated relationships between several personality facets (friendliness, assertiveness, achievement-striving, self-efficacy, and self-consciousness) and mentoring received. By demonstrating the significance of student-initiated mentoring and the influence of specific personality facets on this proactive behavior, our study underscores the importance of providing an environment supportive of mentoring and setting expectations for students early on in their doctoral studies if they are to benefit from mentoring. Future research on the impact of age could also help advance understanding of mentoring among older students as the career landscape continues to change.