Abstract Ni-P, Ni-Co-P and Ni-W-P layers were obtained in galvanostatic conditions, at the current density jdep= 0.200 A·cm-2. The X-ray diffraction method was used to determine phase composition of the layers and the atomic absorption spectrometry was applied to specify their chemical composition. A metallographic, stereoscopic and tunneling microscope and also form Talysurf-type profilograph were used for cross-section and surface morphology characterization of the layers. The behaviour of obtained layers was investigated in the processes of hydrogen and oxygen evolution from 5 mol·dm-3 KOH solution, using voltammetry method. It was ascertained that, introduction of cobalt or tungsten into Ni-P matrix, lead to obtain the layers about very developed surface. Thus obtained layers may be useful in application as electrode materials in electrochemistry.