The main aim of the studies was to establish the parameters of electrolysis corresponding to the lowest value of overpotential of HER (hydrogen evolution reaction). The influence of sodium tungstate concentration, arginine concentration and orientation of applied magnetic field (MF) on composition, morphology, structure, cathodic current efficiency of deposition process and electrocatalytic activity of deposited alloys was examined, Carbon addition to electrodeposited Co-W alloys was made to enhance the electrolytic activity of hydrogen evolution process in 8 mol dm(-3) NaOH at 90 degrees C. The alloys were deposited at pH = 4. The concentration of Na2WO4 center dot 2H(2)O corresponding to the best catalytic activity of the obtained Co-W and Co-W-C alloys was 25 g/l. The positive effect of carbon addition on catalytic activity of hydrogen evolution was observed. The influence of electrodeposition parameters on size of microcracks formed during deposition processes was also investigated. (C) 2012 Elsevier Ltd. All rights reserved.