This study aimed to identify types of natural mentoring relationships that Black adolescents may experience and to connect these relationship types to academic outcomes via social and emotional development. Data were collected from 259 adolescents attending 3 middle schools in a Midwestern metropolitan area. Adolescents reported on whether or not they had a relationship with a natural mentor and answered several questions about characteristics of the relationship, as well as reporting on a number of indicators of positive development. Cluster analyses suggested two different types of natural mentoring relationships among study youth: less connected and more connected. We found that in comparison with youth without a natural mentor, youth who had a more connected natural mentoring relationship had greater student-reported academic engagement via higher social skills and psychological well-being and greater teacher-reported academic engagement via elevated social skills. We found that youth with less connected natural mentoring relationships did not differ from their counterparts without natural mentors on social skills, psychological well-being, or student- or teacher-reported academic engagement. Findings from the current study suggest that characteristics of the mentoring relationship may determine whether these relationships contribute to more positive outcomes among Black youth. Further, findings suggest that social and emotional development may transmit the positive effects of more connected natural mentoring relationships on Black youths' academic engagement.