The effect of Mn substitution for Ni on the structural and electrochemical properties of the La0.7Mg0.3Nb3.4-xCo0.6Mnx (x = 0.0, 0.2, 0.3, 0.4, 0.5) hydrogen storage alloys has been studied systematically. The results by X-ray powder diffraction show that the alloys are all consisted of the (La, Mg)Ni-3 phase and the LaNi5 phase, and the lattice parameters and cell volumes of the component phases all increase with increasing x. P-C isotherms curves reveal that the hydrogen storage capacity increases to a maximum and then decreases with increasing x, but the equilibrium hydrogen pressure decreases continuously with increasing x. The electrochemical studies show that the maximum discharge capacity increases first when x increases from 0.0 to 0.4 and then decreases when x reaches 0.5. The high-rate dischargeability of the alloy electrodes are all rather high increasing from 72.9 (x = 0.0) to 83.8% (x = 0.3) and then decreasing to 78.9% (x = 0.5) at the high discharge current density I-d = 1000 mA g(-1). Meanwhile, the results of the electrochemical impedance spectroscopy, linear polarization, Tafel polarization, and hydrogen diffusion coefficient measurements all indicate that the exchange current density I-0, the limiting current density I-L and the hydrogen diffusion coefficient D of the alloy electrodes also all increase first and then decrease with increasing Mn content in alloys, which signifies that the electrochemical kinetics property of the La0.7Mg0.3Ni3.4-xCo0.6Mnx (x = 0.0, 0.2, 0.3, 0.4, 0.5) hydrogen storage alloys has a most optimum value of Mn content. This phenomena is mainly attributed to the good electrocatalytic activity of Ni element at the surface and the Mn substitution for Ni leads to the increase of Ni content at the surface of alloy electrodes when the amount of Mn substitution is appropriate. (C) 2003 Elsevier B.V. All rights reserved.