Alexithymia refers to difficulties in identifying and describing feelings and is often associated with problematic substance use for a variety of substances. A recent study investigating the relationship between alexithymia and caffeine use found that university students with alexithymia reported typically consuming nearly twice as much caffeine as those without alexithymia. The current study assessed the potential role of caffeine expectancies and craving in mediating this relationship. University students (n = 104) aged 18–30 years, who regularly consumed both caffeine and alcohol, completed the following measures: a demographic questionnaire, Toronto Alexithymia Scale-20 (TAS-20), Beck Anxiety Inventory, Caffeine Expectancy Questionnaire (CaffEQ), Caffeine Consumption Questionnaire, Sensitivity to Punishment and Sensitivity to Reward Questionnaire, and the Alcohol Use Disorders Identification Test. Hierarchical regression and path analyses indicated that caffeine expectancies and caffeine craving mediated the relationship between alexithymia and caffeine consumption. Given that alexithymia is common in samples of clients undergoing treatment for substance dependence for a variety of substances, alexithymia appears to be associated with increased susceptibility to drug cravings—even for a drug as mild in its typical effects as caffeine.