The electrochemical layers with molybdenum were obtained by electrodeposition from citrate bath. The process was carried out under galvanostatic conditions. Structural investigations were conducted by X-ray diffraction method. It was ascertained that electrodeposited Ni-Mo-P alloys are characterized by amorphous structure, Ni-Mo alloys are characterized by nanocrystalline structure whereas Ni+Mo composite layers have a crystalline structure. The chemical composition was determined using X-ray fluorescence spectroscopy method. It was stated that Ni-Mo-P alloys contain 75%Ni, 10%Mo and 15%P, the Ni-Mo alloys contain 90%Ni and 10%Mo, Ni+Mo composite layers contain 90%Ni and 10%Mo. These layers were characterized by electrochemical methods (j=f(E) voltammetry and corrosion resistance by Stem method). The results of corrosion tests show that from among obtained layers the highest corrosion resistances exhibit nanocrystalline Ni-10%Mo alloys.