AB(5)-type rare-earth-based hydrogen storage alloy La0.65Ce0.28Pr0.02Nd0.05Ni3.8Co0.7Mn0.3Al0.2 was prepared by twin-roller rapid quenching process and modified with V2O5. Four samples were obtained with V2O5 contents of 0%, 3%, 6%, 10% in mass fraction, respectively. Their performances were studied with granularity distribution, X-Ray powder diffraction (XRD), scanning electron microscopy (SEM), charging and discharging and cyclic voltammetry. With the modification Of V2O5, the particle size of AB(5) alloy became smaller, but its typical single-phase hexagonal CaCu5-type structure kept unchanged. The discharge capacity increased, the kinetics properties of hydrogen process is improved and the ratio discharge capability was markedly improved.