The study is devoted to comparing the properties of nanosized Ni–Zn–Cu alloy films, which (Ni–Zn–Cu)/(M–M(OH)2)]n multilayer coating consists of, in hydrogen evolution reaction. It is shown that the voltammograms of dissolution of the ternary alloy films contain oxidation peaks of the β-phase of the Zn–Ni alloy, the α-phase of the Cu–Zn alloy, and the alloys of “solid solutions” of Ni in Cu and Cu and Zn in Ni. The advantage of the bilayer deposited in the two-pulse potentiostatic mode over the single-layer film deposited at a potential that is average between the deposition potentials of the bilayer layers is revealed: after additional treatment, the kinetics parameters of the hydrogen evolution reaction in an alkaline medium on its surface are significantly better compared to those on a single-layer film.