The electrocatalytic characteristics of a metal hydride (MH) electrode for advanced Ni/MH batteries include the hydrogen adsorption/desorption capability at the electrode/electrolyte interface. The hydrogen reactions at the MH electrode/electrolyte interface are also related to factors such as the surface area of the MH alloy powder and the nature of additives and binder materials. The high-rate discharge capability of the negative electrode in a Ni/MH battery is mainly determined by the mass transfer process in the bulk MH alloy powder and the charge transfer process at the interface between the MH alloy powder and the electrolyte. In this study, an AB5-type hydrogen-absorbing alloy, Mm (Ni, Co, Al, Mn)5.02 (where Mm denotes Mischmetal, comprising 43.1wt.% La, 3.5wt.% Ce, 13.3wt.% Pr and 38.9wt.% Nd), was used as the negative MH electrode material. The MH electrode was charged and discharged for up to 200 cycles. The specific discharge capacity of the alloy electrode decreases from a maximum value of 290–250mAhg−1 after 200 charge/discharge cycles. A cyclic voltammetry technique is used to analyze the charge transfer reactions at the electrode/electrolyte interface and the hydrogen surface coverage capacity.