Effects of sulfamate-citrate electrolyte pH on the cathodic polarization, content of W in Ni-W alloys, and crystallite grain size are studied by cyclic voltammetry, scanning electron microscopy, and energy dispersion spectroscopy. It is shown that a medium pH has the determining effect on the electrolyte and deposit properties; in a neutral medium, properties of deposits are optimal. A unique dependence of the microhardness on the alloy’s composition is found.