Background Recent studies have linked attention‐deficit/hyperactivity disorder (ADHD) to elevated rates of risky sexual behavior (RSB) in adult samples. The current study tested whether ADHD symptoms were associated with RSB among adolescents, and examined comorbid conduct problems and problematic substance use as joint mediators of this association. Methods ADHD symptoms, conduct problems (oppositional defiant disorder/conduct disorder symptoms), problematic alcohol use (alcohol use disorder symptoms, alcohol use frequency), problematic marijuana use (marijuana use disorder symptoms, marijuana use frequency), and RSB were assessed among an ethnically diverse cross‐sectional sample of adolescents (N = 115; mean age = 14.9 years) involved in the juvenile justice system. Results Bootstrapped mediation models revealed an initial association between ADHD symptoms and RSB that was accounted for fully by the influence of problematic alcohol and marijuana use, but not conduct problems. A follow‐up multiple groups mediation analysis demonstrated that the relationship between ADHD symptoms and RSB emerged only among youth with clinically elevated conduct problems, and that problematic marijuana use fully accounted for this relationship. Hyperactive/impulsive, but not inattentive, symptoms were related to RSB, although the pattern of indirect effects was consistent with the multiple groups analysis. Conclusions The association between ADHD and adolescent RSB is restricted to youth with elevated comorbid conduct problems and reflects the contributions of comorbid marijuana use problems, and to a lesser extent alcohol use problems. Early identification and treatment of these comorbid conditions may be important for the prevention of negative sexual health outcomes among youth with ADHD.