Given that prior research implicates smoking abstinence in increased premenstrual symptoms, tobacco withdrawal, and smoking behaviors, it is possible that women with more severe premenstrual symptoms have stronger expectancies about the effects of smoking and abstaining from smoking on mood and withdrawal. However, such relations have not been previously explored. This study examined relations between premenstrual symptoms experienced in the last month and expectancies that abstaining from smoking results in withdrawal (i.e., smoking abstinence withdrawal expectancies), that smoking is pleasurable (i.e., positive reinforcement smoking expectancies), and smoking relieves negative mood (i.e., negative reinforcement smoking expectancies). In a cross-sectional design, 97 non-treatment seeking women daily smokers completed self-report measures of smoking reinforcement expectancies, smoking abstinence withdrawal expectancies, premenstrual symptoms, mood symptoms, and nicotine dependence. Affect premenstrual symptoms were associated with increased negative reinforcement smoking expectancies, but not over and above covariates. Affect and pain premenstrual symptoms were associated with increased positive reinforcement smoking expectancies, but only affect premenstrual symptoms remained significant in adjusted models. Affect, pain, and water retention premenstrual symptoms were associated with increased smoking abstinence withdrawal expectancies, but only affect premenstrual symptoms remained significant in adjusted models. Findings from this study suggest that addressing concerns about withdrawal and alternatives to smoking may be particularly important in women who experience more severe premenstrual symptoms, especially affect-related changes.