The current study examined important predictors of substance use during early adolescence. The authors hypothesized that adolescents' relationships with key adults (i.e., teachers and parents) influence their choices to use substances indirectly through links with their decisions regarding peer groups. A total of 461 middle school students from an affluent suburban community completed self-report measures of authoritative parenting, perceived social support from teachers, affiliation with rule-breaking and substance-using peers, and frequency of alcohol, cigarette, and drug use. Results of structural equation modeling supported the hypothesized model. Authoritative parenting and teacher support accounted for 31% of the variance in affiliation with deviant peers which, in turn, accounted for 27% of the variance in adolescent substance use; direct paths from parenting and teacher support to substance use were not indicated. Implications for school psychologists' involvement in substance use prevention and intervention are discussed. (Contains 1 figure, 3 tables, and 1 footnote.)