The structure and electrochemical characteristics of melted composite Ti0.10Zr0.15V0.35Cr0.10Ni0.30 + x% LaNi4Al0.4Mn0.3Co0.3 (x = 0, 1, 5) hydrogen storage alloys have been investigated systematically. XRD shows that though the main phase of the matrix alloy remains unchanged after LaNi4Al0.4Mn0.3Co0.3 alloy is added, a new specimen is formed. The amount of the new specimen increases with increasing x. SEM-EDS analysis indicates that the V-based solid solution phase is mainly composed of V, Cr and Ni; C14 Laves phase is mainly composed of Ni, Zr and V; the new specimen containing La is mainly composed of Zr, V and Ni. The electrochemical measurements suggest that the activation performance, the low temperature discharge ability, the high rate discharge ability and the cyclic stability of composite alloy electrodes increase greatly with the growth of x. The HRD is controlled by the charge-transfer reaction of hydrogen and the hydrogen diffusion in the bulk of the alloy under the present experimental conditions.