Abstract Background Adult Attention-Deficit/Hyperactivity Disorder (ADHD) is associated with high rates of comorbid substance use disorders, and cigarette smoking has a particularly high prevalence in this population. However, there is an ongoing debate as to whether this tobacco use is an attempt at “self-medication” or due to behavioral disinhibition. There is a surprising lack of qualitative studies that investigate the subjective perceptions of adults with ADHD regarding cigarette smoking. The present study was designed to fill this gap in the literature. Methods We recruited twelve adult patients with ADHD and comorbid tobacco use from our ADHD consultation service, an outpatient facility of the Zurich University Psychiatric Hospital. Subjects were interviewed using qualitative methodology, and Mayring's qualitative content analysis was used to evaluate findings. Results We identified two explanatory models linking ADHD and tobacco use: smoking as an attempt at self-medication and “smoking as a social behavior”. On one hand, subjects considered tobacco a therapeutic aid, reporting positive effects on “inner tension” and cognitive function, and noted possible antidepressant properties as well. On the other hand, subjects considered smoking to enhance social functioning and to have a positive impact on interpersonal relationships. The majority believed that stimulant medications offered only a transient decrease in patterns of tobacco use because their ability to reduce nicotine cravings wore off quickly. Others believed that stimulants had no effect or even reinforced cigarette use. Conclusions Participants had different views about the link between cigarette smoking and ADHD. While the majority thought of nicotine as a sort of therapy, viewing smoking as a way to self-medicate symptoms of ADHD, motivations for nicotine use were also related to self-image, desire to belong to a peer-group, and a drive to undermine perceived social norms. Ultimately, these findings can be used by clinicians to improve treatment alliance and collaboration.