Adults with attention-deficit/hyperactivity disorder (ADHD) are at higher risk to use substances than their nonclinical peers. Increased levels of impulsivity are generally thought to contribute to their increased levels of risk. Impulsivity is a multifaceted construct, however, and little research to date has attempted to identify which facets of impulsivity contribute to the increased rates of substance abuse among individuals with ADHD. The current study examined the relation among ADHD symptom clusters (i.e., hyperactivity/impulsivity and inattention), substance use rates (i.e., alcohol use, nicotine use, and marijuana use), and personality processes associated with impulsive behavior in a group of young adults. Participants were 361 undergraduate students. Both symptom clusters were positively associated with rates of substance use. Specifically, hyperactive/impulsive symptoms were associated with alcohol and nicotine use, and inattentive symptoms were associated with alcohol use. Several pathways from hyperactive/impulsive symptoms to alcohol, nicotine, and marijuana use via specific facets of impulsivity were identified. These findings have implications for understanding the relation between ADHD symptoms and substance use, as well as clinical implications for preventing and treating substance use problems in individuals with symptoms of ADHD.