Abstract The electrolysis modes affect on the quantitative and phase composition of the ternary Fe-Co-W and Fe-Co-Mo coatings is studied. It was established that the distribution of refractory components over the thickness of the coating varies in the opposite way with increasing duration of electrolysis – the molybdenum content increases and the tungsten one decreases. Amorphous-crystalline structure of alloys has been visualized by X-ray spectroscopy, including inter-metallic phases Co7W6, Fe7W6, Fe7Mo, Fe7Co, FeCo along with α-Fe and Fe3C. The size of coherent-scattering region of the amorphous part is of 6–8 nm. The formation of metallic tungsten and molybdenum additional phases has been detected for alloys deposited at pulse current which contributes microhardness Hμ increase up to 700 compared with direct current mode. Magnetic characteristics of Fe-Co-W(Mo) films were measured depending of deposition time. It was concluded that the content of magnetic phases in upper layers of Fe-Co-W deposits is higher than in the bottom ones and superior Fe-Co-Mo coatings. It qualitatively corresponds to W(Mo) content changes over the thickness.