Sputtering method was used to prepare Ni-Mo alloy electrodes for hydrogen production in alkaline solution. The influences of the working pressure during deposition and the substrate temperature on the electrochemical behavior of electrode were characterized by steady-state polarization plot and Tafel polarization curve measurements. And the physical properties of electrodes were characterized by XRD, SEM, AFM and EDS. It is found that the overpotential is significantly influenced by the working pressure which affects critically the electrode surface morphology, and two Tafel regions are observed for each sample. The overpotential value does not change very much with the substrate temperature. The XRD results indicates that the electrodes should be considered nanocrystalline. Thornton model for the microstructure of sputter-deposited electrodes is referred to explain the observed microstructure change. Sputtering method was used to prepare Ni-Mo alloy electrodes for hydrogen production in alkaline solution. The influences of the working pressure during deposition and the substrate temperature on the electrochemical behavior of electrode were characterized by steady-state polarization plot and Tafel polarization curve measurements. And the physical properties of electrodes were characterized by XRD, SEM, AFM and EDS. It is found that the overpotential is significantly influenced by the working pressure which affects critically the electrode surface morphology, and two Tafel regions are observed for each sample. The XRD results indicate that the electrodes should be considered nanocrystalline. Thornton model for the microstructure of sputter-deposited electrodes is referred to explain the observed microstructure change.