This study was designed to identify different risk models associated with non-use, first use, and prior substance use among a group of early adolescents. A total of 582 students completed a self-report questionnaire at the beginning and end of sixth grade. Nine predictor variables were used in discriminant function analysis to classify adolescents into three groups. Five variables distinguished non-users (never used by the end of sixth grade) and new users (first used during sixth grade) from prior users (first used before sixth grade). Prior users were found to have weaker decision making skills, more susceptibility to peer pressure, more negative perceptions of school, less confidence in their skills, and an increased likelihood of being male. A second function indicated that new users were similar to prior users in that they had less positive peer relations, were more likely to come from single parent families, and had less knowledge about alcohol and drugs than did non-users. The similarities and differences between new and prior users have implications for future research and prevention programming.