The Medication Adherence Questionnaire (MAQ) is a scale used to evaluate adherence to medications. The present study assessed the factor structure and validity of the MAQ with cigarette smokers. A principal components analysis was conducted on MAQ scores from a sample of smokers presenting for treatment in a clinical trial of naltrexone and nicotine patch for smoking cessation (N = 385). Indices of convergent and predictive validity were tested using electronic medication caps for naltrexone, nicotine patch counts, plasma drug levels of naltrexone, and treatment outcomes. The principal components analysis revealed two factors. Factor 1, labeled "unintentional nonadherence," measured the extent to which individuals were nonadherent because they were careless or forgot to take their medications. Factor 2, labeled "purposeful nonadherence," assessed nonadherence related to purposefully stopping medication use after feeling better or worse. Only the second factor was shown to have good convergent and predictive validity. Specifically, this factor was related to pill-taking behavior measured with electronic medication caps and drug plasma levels and nicotine patch use based on nicotine patch count data, and it was associated with smoking cessation outcome. Thus the purposeful nonadherence factor of the MAQ may be used as a brief screening tool for medication adherence with cigarette smokers seeking treatment. Information obtained with this questionnaire could be used to counsel patients regarding the importance of medication adherence.