Hydrological risk analysis and management entails multivariate modeling which requires modeling the structure of dependence among different variables. Vine copulas have been increasing applied in multivariate modeling wherein the selection of vine copula structure plays a critical role. This study develops a mutual information (MI)-based sequential approach to select a vine structure which is model-independent. Then, an MI-based approach for hydrological dependence modeling is developed. An application of drought characterization is utilized to show the performance of the proposed approach. Results indicate that the MI-based approach satisfactorily models different kind of dependence structure.