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. Measurement models, measurement invariances, and concurrent and convergent validity with psychosocial and psychopathological variables were tested. Results (1) confirmed the B-WISDM dimensionality in 11 first-order intercorrelated factors; (2) showed its measurement invariance for the types of smokers; (3) showed that tobacco dependence is only and positively predicted by primary dependence motives, 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, and weight control with eating disorders. Thus, external validity of the B-WISDM is extended to non-daily smokers. Specific associations of B-WISDM with smoking-related psychological potentially make it a very useful diagnostic tool to support smokers toward quitting.