Polysubstance use is related to elevated risk for adverse outcomes but remains understudied among early adolescents. This study focused on a cross-sectional (N = 1568) primarily Black (79%) sample of eighth grade students living in urban communities (Mean age = 13.8, SD = 0.68) to identify subgroups based on adolescents' reports of lifetime and past 30-day substance use. It also examined subgroup differences in individual, peer, caregiver, and community risk and promotive factors. Latent class analysis identified four subgroups: "Non-use" (73.7%), "Alcohol Use" (5.8%), "Lifetime Use" (13.2%), and "Polysubstance Use" (7.2%). There were no sex differences in subgroup membership when accounting for differential item functioning. The polysubstance use subgroup reported the highest levels of risk (e.g., delinquency) and lowest levels of promotive factors (e.g., caregiver knowledge). Findings inform our understanding of polysubstance use patterns during early adolescence within a primarily Black urban sample and suggest implications for future research.