Key psychosocial risks associated with adolescent smoking are well established. However, the ways in which the key risks of impulsivity, peer cigarette smoking, and self-reported use of alcohol interact to predict adolescent cigarette smoking is largely unknown. A sample of 210 Australian middle high school students aged 14-16 completed questionnaires. A 3-way interaction of impulsivity, peer cigarette smoking and self-reports of alcohol use significantly predicted smoking, and relegated simpler interactions to nonsignificance. Adolescents with two and three elevated risk factors were 17 and 40 times more likely to be recent smokers, respectively, compared with those who evidenced no elevated risk factors. Common prevention strategies involving alcohol refusal skills training may need refinement to take into account the complexity of risk factor interactions.