Activated carbon (AC) and carbon nanotubes (CNTs) were used to fabricate resin/carbon composite electrodes (D314/AC and D314/CNTs). The adsorption characteristics of vanadium (V) on the two electrodes under different pH and voltage conditions were compared in capacitive deionization. Physical and electrochemical studies on the electrodes indicated that micropores and mesopores are well balanced in D314/AC, but mesopores are dominant in D314/CNTs. D314/CNTs showed higher specific capacitance and higher ion adsorption capacity than D314/AC. This study indicated that the adsorption performance of composite electrodes for V is affected by the electrode material, especially the pore properties.