Interrupted education of adolescent mothers remains a major concern, but limited evidence-based programming exists to support postpartum schooling of this group. This study aimed to better understand the factors that render some adolescent mothers vulnerable to school non-enrollment, and how to reduce these risks. Data from 1,046 adolescent and young mothers (10-24 years) from rural and urban communities in South Africa's Eastern Cape was obtained through a questionnaire containing validated and study-specific measures relating to sociodemographic characteristics, schooling, relationships, violence exposure, and health. Using latent class analysis, we explored emerging latent groups and their relationship to mothers' enrollment in school, college, or tertiary education. The analyses revealed three distinct groups of mothers: The 'most disadvantaged' subgroup (39%) experienced multiple risks, including food insecurity, living in informal housing, lacking positive relationships with their caregiver, and the highest distance to school; The 'disadvantaged' subgroup (44%) did not experience food insecurity whilst reporting better caregiver relationships and lower distance to school. However, this group still showed high probabilities of residing in informal housing and in communities that expose them to violence; A 'least disadvantaged' subgroup (17%) was largely unaffected by economic and community risks and experienced good caregiver relationships. Compared to the most disadvantaged mothers, the least disadvantaged mothers showed the highest probability of being enrolled in education (65% versus 45%). Adolescent motherhood can impede continued enrollment in education and individual-centered interventions alone might not be sufficient to mitigate the risks for non-enrollment. Services and provisions that address severe poverty and improve family relationships might provide an opportunity to positively influence schooling among adolescent mothers.