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Purpose While previous research has examined the effectiveness of peer mentoring from the mentee's perspective, more research is needed to uncover how and why the interplay of the peer-mentoring relationship in a virtual format, especially for racial and ethnic minority (REM) women in historically Black colleges and universities (HBCUs) seeking a science, technology, engineering and mathematics (STEM) degree, impacts STEM success. This study seeks to address weaknesses in the mentoring literature by presenting a thorough and thick description of the peer mentoring experience for REM women in HBCU pursuing STEM degrees. Design/methodology/approach A multi-site case study approach (Yin, 2014) was employed to explore to what extent, if at all, and how did participating in the virtual STEM peer-mentoring experience influence peer mentees' STEM beliefs, interests, skills and behaviors. Findings Findings demonstrated that the experiences of undergraduate REM women mentees supported engagement in virtual STEM peer mentoring as it was beneficial to developing a sense of belonging, enhancing interest in STEM, encouraging STEM identity, building STEM self-efficacy and, ultimately, promoting STEM persistence. The current study provides a rich picture of how and why peer mentoring is perceived as effective by mentees in STEM programs at HBCUs. Originality/value The findings from this study contribute greatly to the body of knowledge and will serve as a foundational model on which future VSTEM PM relationships can be built and fostered among other HBCUs, with the potential to broaden participation in STEM.