This study investigated associations between natural mentoring relationships and academic performance via psychological distress among underrepresented college students attending an elite predominantly White institution (PWI). Specifically, this study explored whether the quantity of natural mentors possessed upon college entry, the retention of natural mentors across the first year of college, and overall changes in the number of natural mentors possessed during the first year of college predicted improvements in students' semester grade point averages (GPAs) via reductions in psychological distress. Participants in this study included 336 first‐year undergraduate students attending a selective PWI. Students were eligible to participate in this study if they were first‐generation college students, students from economically disadvantaged backgrounds, or students from underrepresented racial/ethnic minority groups. Results of this study indicated that a greater number of retained natural mentoring relationships across the first year of college were associated with improvements in students' GPAs via reductions in symptoms of depression from the Fall to Spring semester. The results of this study suggest that institutional efforts to support the maintenance of preexisting mentoring relationships may be an effective approach to promoting the academic success of underrepresented college students during the first year of college.