Objective: Attention-deficit/hyperactivity disorder (ADHD) is associated with an increased smoking prevalence and impairments in executive function, which may negatively affect the validity of self-reported smoking rates. This study compares the utility of self-reported smoking with salivary cotinine in adult smokers and nonsmokers with and without ADHD. Methods: Participants (N = 82) were adult smokers and nonsmokers with and without ADHD (n = 35 ADHD and n = 47 controls) from an observational study. Odds ratios (ORs) for accuracy of self-reported smoking compared to salivary cotinine were calculated using diagnosis (ADHD vs. control), gender, age, education, employment, and number of cigarettes per day as predictors. Post-hoc analysis stratified sensitivity, specificity, and accuracy of self-reported smoking in individuals with ADHD and without ADHD. Results: The initial analysis identified education as a significant independent predictor of odds of accuracy, OR = 6.22, p = .013, after adjusting for diagnosis, gender, age, employment, and cigarettes per day. Post-hoc analysis revealed that sensitivity, specificity, and accuracy of self-reported smoking was 100% for individuals with ADHD who had more than high school education compared to those with high school or less, which was 83.3%, 45.5%, and 65.2%, respectively. Self-reported smoking of control participants with greater than a high school education had a sensitivity of 85.7%, a specificity of 91.7%, and an accuracy of 88.5%. Control participants with a high school or lower education had a sensitivity of 54.6%, a specificity of 90%, and an accuracy of 71.4% for their self-reported smoking. Conclusions: Individuals with ADHD and high school or lower education showed the lowest specificity and accuracy in their self-reported smoking, which may affect documented smoking prevalence rates. This is a secondary analysis of data collected as part of a clinical trial registered as NCT00915798 at www.clinicaltrials.gov .