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Two consistent findings in the research on adolescent substance use show that both adverse childhood experiences (ACEs) and peer influences significantly predict early tobacco, alcohol, and illicit drug use. However, less research considers how peer and community influences contribute to the association between ACEs and early substance use. This study addresses these gaps in the literature by using multi-level, longitudinal data from the Project on Human Development in Chicago Neighborhoods (PHDCN). First, this study analyzes whether unstructured socializing and peer substance use mediate the association between ACEs and substance use; second, if youth with a history of ACEs are more vulnerable to peer influences; and third, if neighborhood collective efficacy further moderates peer influences for youth with differing levels of ACEs. Three main findings emerged from this study. First, unstructured socializing and peer substance use significantly mediated the association between adverse childhood experiences and binge drinking, smoking cigarettes, and illicit drug use. Second, youth with a history of adverse childhood experiences were more likely to smoke and use drugs in the presence of these peer contexts compared to their counterparts. Third, neighborhood collective efficacy further structures how adverse childhood experiences moderate the effect of peer influences. Youth with a more extensive history of adverse childhood experiences living in high collective efficacy neighborhoods were the most likely to smoke and use drugs when exposed to substance-using peers or in unstructured social settings.