Composite electrodes prepared by cation exchange resins and activated carbon (AC) were used to adsorb V(Ⅳ) in capacitive deion-ization (CDI). The electrode made of middle resin size (D860/AC M) had the largest specific surface area and mesoporous content than two other composite electrodes. Electrochemical analysis showed that D860/AC M presents higher specific capacitance and electrical double layer capacitor than the others, and significantly lower internal diffusion impedance. Thus, D860/AC M exhibits the highest adsorption capacity and rate of V(Ⅳ) among three electrodes. The intra-particle diffusion model fits well in the initial adsorption stage, while the liquid film diffusion model is more suitable for fitting at the later stage. The pseudo-second-order kinetic model is suited for the entire adsorption process. The ad-sorption of V(Ⅳ) on the composite electrode follows that of the Freundlich isotherm. Thermodynamic analysis indicates that the adsorption of V(Ⅳ) is an exothermic process with entropy reduction, and the electric field force plays a dominant role in the CDI process. This work aims to improve our understanding of the ion adsorption behaviors and mechanisms on the composite electrodes in CDI.