Hydrogen storage composite alloy Ti0.10Zr0.15V0.35Cr0.10Ni0.30–10% LaNi3 was prepared by two-step arc-melting to improve the electro-catalytic activity and the kinetic performance of Ti-V-based solid solution alloy. The electrochemical properties and synergetic effect of the composite alloy electrode were systematically investigated by using X-ray diffractometry, field emission scanning electron microscopy, energy-dispersive spectrometry, electrochemical impedance spectroscopy and galvanostatic charge/discharge test. It is found that the main phase of the composite alloy is composed of V-based solid solution phase with a BCC structure and C14 Laves phase with hexagonal structure, while the secondary phase is formed in the composite alloy. The comprehensive electrochemical properties of the composite alloy electrode are significantly improved. The activation cycle number, the maximum discharge capacity and the low temperature dischargeability of the composite alloy are 5 cycles, 362.5 mA-h/g and 65.84% at 233 K, respectively. It is suggested that distinct synergetic effect occurs in the activation process, composite process, cyclic process and discharge process at a low or high temperature under different current densities, in the charge–transfer resistance and exchange current density.