Objectives: The main objective of this study was to examine the role of psychological factors affecting college students' smoking behavior. We considered 3 psychological factors in this study - depressive symptoms, novelty seeking personality, and stress, which are common among learners in institutions of higher learning. Furthermore, we also considered the moderating effect of tobacco advertising receptivity and health behavior. Methods: In this study, we used a cross-sectional research design, wherein data were collected through a survey questionnaire, designed on a Likert scale. We received 160 responses for data analysis. Our primary analysis used partial least squares (PLS). Results: Depressive symptoms, novelty seeking personality, stress, and tobacco advertising receptivity had significant positive relationships with college students' smoking behavior; however, pro-health behavior had a negative effect on smoking behavior. Conclusion: Our results reveal a major role of depressive symptoms, novelty seeking personality and stress in shaping the smoking behavior of college students in China. Additionally, the moderating variables of tobacco advertising receptivity and health behavior showed considerable impact, as both showed a positive influence on psychological factors and smoking behavior of college students. Finally, our results provide insights for practitioners to devise strategies to address smoking behavior in college students.