Ni-Mo and Ni+Mo coatings were prepared by electrodeposition under the galvanostatic conditions, in such a manner that the coatings contain the same quantity of molybdenum. The electrochemical activity of these coatings was studied in the process of hydrogen evolution reaction (HER) from 5 M KOH solution using steady-state polarization and electrochemical impedance spectroscopy (EIS) methods. Basing on the results of EIS measurements, the rate constants of the HER as well as the surface roughness factors were determined. It was found that Ni+Mo composite coating is characterized by enhanced electrochemical activity towards hydrogen evolution as compared with Ni-Mo alloy coating. Improvement of the electrocatalytic performance of Ni+Mo composite coating could be attributed to the increase in its real surface area as well as to the catalytic effect in points of contact of molybdenum and nickel matrix. Thus obtained composite coating may be useful in application as electrode materials for the hydrogen evolution reaction.