This paper is devoted to the investigation of main peculiarities of hydrogen evolution reaction on the electrodeposited Ni-P alloys in deaerated 0.05M H2SO4 solution. It was established that polarization decreases and the rate of HER increases significantly with rising of phosphorus content from 0 to 12.6 wt.%. The experimental data were interpreted from the point of structure and real surface area of the deposited coatings as well as reaction mechanism.