Introduction: This study investigates the validity of the Brief Wisconsin Inventory of Smoking Dependence Motives (B-WISDM) among French daily and non-daily university student smokers, and its associations with psychological variables related to smoking, namely attitude, social norms, perceived behavioral control, identity, and psychopathological variables, namely eating disorders, anxiety, and depression. Methods: We tested three measurement models of the B-WISDM using robust confirmatory factor analysis, measurement invariance for daily vs. non-daily smokers, and predictive and convergent validity using a bootstrap multivariate regression model with tobacco dependence and psychological variables as outcomes. Results: The results (1) confirmed the B-WISDM dimensionality in 11 first-order intercorrelated factors among university students; (2) showed the B-WISDM measurement invariance for the types of smokers; (3) showed that tobacco dependence is only and positively predicted by primary dependence motives, namely tolerance, craving, and lack of control, which confirm that they are core components of tobacco dependence; and (4) highlighted specific associations between smoking motives and psychological variables, such as smoking identity and perceived behavioral control with some primary dependence motives, social goads with social norms, weight control with eating disorders, and affiliative attachment and affective enhancement with psychopathological variables. Conclusions: In addition to showing the French B-WIDSM good psychometric qualities among university students, this study extends the B-WIDSM external validity to non-daily smokers, meaning that tobacco dependence motivations are conceptually identical for (non-)daily student smokers, and shows specific associations of psychological variables with some smoking motives, which is of great interest for inducing smoking reduction.