Thin films of Mg2−x Al x Ni alloys have been prepared by magnetron sputtering, and the effects of partial substitution of Al for Mg on the electrochemical properties of the films were studied. EIS results indicate the rate-limiting process for the thin film hydride electrode is the charge transfer reaction during the process of total discharge. A theoretical model has been derived for the impedance of a thin film hydride electrode based upon the assumption that hydrogen diffusion is neglected in the electrode. The charge-transfer reaction rate at the electrode surface and hydrogen diffusivity in the Mg2−x Al x Ni thin film hydride electrodes were observed to initially decrease then increase with increasing Al content. Results from capacitance measurements indicate n-type semiconductor properties for the corrosion layer during the charge–discharge process. Hydrogen atom and OH− transfer became more difficult with increasing Al content until x =0.3, after which a significant drop in the barrier resistance was observed.