Objective: In the present study, we sought to establish a link between suicidal ideation (SI) and smoking in college students, determine whether psychopathology accounted for the association, and determine whether smoking expectancies were moderators. Participants: Participants (N = 607) were identified as nonsmokers, ex-smokers, infrequent smokers, or daily smokers. Methods: Participants were assessed for smoking patterns, smoking expectancies, psychopathology, SI, and past suicide attempts. Results: Daily smokers had the highest level of SI. There was a dose-response relationship between smoking and SI, such that the higher the daily smoking rate, the greater the SI, even when controlling for depression, alcohol use, and drug use. Trend-level results indicated that at lower smoking rates, elevated smoking-related negative affect reduction (NAR) expectancies were associated with lower SI, while elevated NAR expectancies in combination with higher smoking rates were associated with greater SI. Conclusion: Smoking cessation programs for college students should screen for SI.