Principles of Fe-Co-W, Fe-Co-Mo, and Co-Mo-Zr alloys’ electrodeposition from complex based on Fe (III) citrate and citrate-pyrophosphate electrolytes are discussed. It is shown that deposition of ternary alloys proceeds through competitive reduction of cobalt and tungsten (molybdenum) with iron. With increasing ligand concentration, coatings are enriched with a refractory component; however, increasing current density favors a reverse trend. The effect of both current density and pulse on-/off-time on the quality, composition, and surface morphology of the electrolytic alloys was determined. The application of pulsed electrolysis provides increasing tungsten content up to 13 at.% and Mo, 38 at.%, at current efficiency of 70–75%. It was found that the alloying metal content in Co-Mo-Zr coating depends on the current density and on-/off-times extremely, and maximum Mo and Zr content corresponds to 4–6 A/dm2 and on-/off-time of 2–10 ms. Globular surface of Fe-Co-W(Mo) and Co-Mo-Zr coatings is caused by refractory metal incorporation, and crystalline and amorphous parts of the structure are visualized by X-ray spectroscopy, including intermetallic phases Co7W6, Fe7W6, Fe7Мо, Fe7Co, and FeCo along with α-Fe and Fe3C. The crystallite size of the amorphous part is nearly 7–8 nm. It was detected that the coercive force for synthesizing Fe-Co-W and Fe-Co-Mo films is 50–60 Oe and 7–10 Oe, respectively, which corresponds to the soft magnetic materials. Corrosion resistance of the coatings Fe-Co-W and Fe-Co-Mo is 1.3–2.0 orders of magnitude higher than the substrate parameters as follows from data of polarization resistance method and electrode impedance spectroscopy. It was shown that Fe-Co-W, Fe-Co-Mo, and Co-Mo-Zr alloys exhibit superior catalytic properties in hydrogen electrolytic evolution from acidic media which are not inferior a platinum electrode. The deposits Co-Mo-Zr with zirconium content 2–4 at.% demonstrate high catalytic properties in the carbon(II) oxide conversion. This confirms the efficiency of materials as catalysts for the gaseous wastes purification and gives the reason to recommend them as catalysts for redox processes activating by oxygen as well as electrode materials for redox batteries.