Purpose: The purpose of this paper is to examine how a peer mentoring relationship may support provisional psychologists engaged in postgraduate education in Australia. The theoretical lens for this study draws from the real relationship framework and significant events literature. Design/methodology/approach: Quantitative and qualitative data were obtained via a web survey from a sample of 23 mentors and 41 mentees. Participants had engaged in a one-year peer mentoring program on a volunteer basis. The survey contained measures of functions of mentoring, perceived genuineness and realism in the relationship, and overall satisfaction with peer mentoring. Participants also provided accounts of helpful events, hindering events and open feedback. Findings: Perceived satisfaction was significantly correlated with greater genuineness and realism in the relationship. Satisfaction was associated with psychosocial and clinical functions of mentoring for both mentors and mentees, and career functions for mentees only. Qualitative findings indicated that the most helpful events included psychosocial support, mutual understanding and skill development. The most frequent hindering events were logistics/time, lack of structure and mentor technique/activity. Practical implications: Peer mentors show great promise for supporting provisional psychologists. Recommendations for higher education providers include providing peer mentors with guidance regarding the importance of psychosocial support, clinical skill development and creating genuine and real relationships. Peer mentor training would also benefit from the inclusion of career development strategies and psychoeducation on transference. Originality/value: This study is the first to apply the real relationship framework and significant events analysis to the psychology peer mentoring context.