The aim of this work was to investigate the possibility of preparation of the composite Cr-MoO2 coatings onto steel and titanium substrates as cathode materials with high selective properties which imply the suppression of hypochlorite reduction as a side reaction during hypochlorite commercial production. The electrodes were prepared by simultaneous deposition of chromium and suspended MoO2 particles on titanium substrate from acid chromium (VI) bath. The current efficiency for electrodeposition of the composite coatings did not vary significantly with the concentration of suspended MoO2 particles. The content of molybdenum in the deposits was relatively low (0.2-1.5 at.%) and increased with increasing the concentration of suspended MoO2 particles in the bath, in the range from 0 to 10 g dm(-3). With further increase in the concentration of MoO2, the content of molybdenum in the coating varied insignificantly. X-ray photoelectron spectroscopy-XPS and EDS analysis were applied to analyze elemental composition and chemical bonding of elements on the surface and in the sub-surface region of obtained coatings. When the concentration of MoO2 particles in the bath was raised above 5 g dm(-3), the appearance of the coating changed from the typical pure chromium deposit to needle-like deposit with the appearance of black inclusions on the surface. XPS analysis and corresponding Cr 2p spectra showed the presence of chromium oxide, probably Cr2O3 with Cr(3+) valence state on the surface and in the sub-surface region of Cr-MoO2 coatings. Investigation of the current efficiency for the hydrogen evolution reaction (HER) on Cr-MoO2 cathodes showed that it increased with the increase of the content of MoO2 particles in the coating, exceeding the value of 97% in the solution with the hypochlorite concentration of 0.21 mol dm(-3). Under the same conditions, the current efficiency for the HER on Ti and Ti/Cr cathodes is very low (approximate to 20%), and corresponding polarization curves confirmed the fact that the side reaction of hypochlorite reduction takes place in the diffusion-controlled regime on these electrodes. The high selectivity of Cr-MoO2 coating is probably caused by the presence of chromium oxide (hydroxide) formed at the surface of the coating during co-deposition of Cr and MoO2 particles, which prevents hypochlorite reduction on the cathode during the HER. (C) 2013 Elsevier Ltd. All rights reserved.