The phase structures and the electrochemical properties of the TiV-based hydrogen storage electrode alloy Ti0.8Zr0.2V2.4 Mn0.48Cr0.72Ni0.9 after rapid solidification have been studied. It is found by XRD analysis that the alloy mainly consists of C14 Laves phase with hexagonal structure and V-based solid solution phase with BCC structure. The rapid solidification leads to the decrease in content of the C14 Laves phase in the alloy. Electrochemical analyses show that the rapid solidification reduces the maximum discharge capacity, increases the activation cycles, elevates the surface reaction resistance and worsens the kinetic properties of the alloy electrode. However, the cyclic stability of the alloy electrode is improved greatly after rapid solidification.