A clinic-referred sample of 109 children with attention-deficit/hyperactivity disorder (ADHD) was followed into adolescence for the ascertainment of alcohol and other drug use and abuse. Learning disability (reading or math) in childhood was examined as a predictor of adolescent substance use and substance use disorder for alcohol and marijuana. No statistically significant group differences for children with LD versus those without LD emerged even after using different methods to compute LD. IQ/achievement discrepancy scores were similarly not predictive of later use or abuse. However, children with ADHD who had higher IQs and higher levels of academic achievement in childhood were more likely to try cigarettes, to smoke daily, and to have their first drink of alcohol or first cigarette at an early age. Children with ADHD who had higher reading achievement scores were less likely to have later alcohol use disorder. Although these findings are necessarily preliminary, due to the small number of children interviewed, the pattern of results suggests that level of cognitive functioning—rather than discrepancy between IQ and achievement—is important for the prediction of later substance use and abuse, at least in this clinic-referred sample of children with ADHD. Further, different mechanisms of risk related to cognitive functioning may be operating for experimentation with legal drugs such as alcohol and tobacco, regular cigarette smoking, and problematic alcohol use.