Cognitive-Experiential Self-Theory (CEST) emphasizes the dual roles of rational and experiential thinking, with individuals having varying preferences for each style. This study explored the relationship between these constructs, illustrating the value of the derived model in addictive behavior, as illustrated by smoking. Data were extracted from a study of the predictors of men's health behavior. Participants comprised 212 Australian men (aged 25-65. years) who completed a self-report questionnaire which assessed thinking styles and recorded smoking status. Rational and experiential data were subjected to cluster analysis and median splits to identify logical subgroups based on participants' dual responses. The four derived clusters were more representative of smoking status than groups defined by median splits. In general, both smokers and ex-smokers preferred experiential thinking and non-smokers preferred rational thinking. There was a strong tendency for smokers to report both low rational and high experiential thinking. The use of cluster analysis advanced the evaluation of the interactive nature of rational and experiential thinking by allowing an empirical test of their potential relationship. The thinking profiles reported represent an advance in the assessment of CEST which may provide a useful model for applications in fields both related to, and beyond, addiction.