Background: Smoking has resulted in numerous deaths in China. Data indicate that 21% of college students in China are smokers. Objective: This study aimed to examine the smoking-related behaviors of undergraduates, as influenced by knowledge, attitude, social pressure, and environmental constraints. Method: A convenience sampling of 412 fresh undergraduates from two universities in the University Town in Chongqing, China was recruited. Chi-square tests were used to compare the smoking-related variables between smokers and non-smokers. Moreover, logistic regression was used to examine the factors that associated with smoking status in undergraduates. Results: Smokers and non-smokers differ in terms of knowledge, attitudes toward smoking, participation in tobacco promotional activities, and sources of social pressure. Logistic regression model identified that sex, living cost, five smoking-related attitudes of “Smoking is pleasurable, Smoking relaxes me, Smoking makes me look strong, Smoking is a waste of money, Smoking can help me study better”, the social pressure “Smoking brings comfort during celebration”, and the environmental constraints “How did you get your cigarettes in the past 30 days?” are significantly associated with smoking. Conclusions: The findings provide a better understanding of the epidemic of smoking among fresh undergraduates in Chongqing, China. This study provides more detailed consideration of the implications for the WHO Framework Convention on Tobacco Control (FCTC) policies, especially on restriction of retail sales outlets and tobacco promotion activities near universities in China.