Underrepresented college students, particularly those attending a predominantly White institution (PWI), face unique challenges that undermine well-being and academic performance. However, support from natural mentors may mitigate the harms caused by these challenges and promote more positive college adjustment. The current study investigated how cumulative appraisal support, emotional support, informational support, and instrumental support from up to five natural mentors during students' first year of college were related to various concurrent and longitudinal outcomes. We found that 3 out of 4 types of social support were related to more positive, concurrent psychological or academic outcomes. Based on the results, we suggest that natural mentorship during students' first year of college has the potential to set a foundation for more positive adjustment among underrepresented students.