This study describes natural mentoring among preadolescent children placed in out‐of‐home care and examines the association between natural mentoring and demographic, maltreatment, placement, and psychosocial characteristics. Cross‐sectional data from a sample of 263 children and their out‐of‐home caregivers were analyzed. Caregivers rated children's social skills, and children reported on their perceived opportunities and attachment to peers and adults, including natural mentors. About half the sample endorsed having natural mentors, with school personnel being the most common type of mentor. Children with natural mentors were older, more likely to be living in congregate care, and had stronger attachment to friends. Marginally significant findings suggested that children with natural mentors had been in out‐of‐home care for fewer months, and children who were sexually abused were less likely to have natural mentors with whom they had current contact. Future research is needed that examines the longitudinal course of natural mentoring among this population.