Copper(II) ferrite is synthesized by the co-precipitation method in the absence and in the presence of polyvinyl alcohol which is followed by thermally treatment at 300, 500, 700, and 900°С. The specific surface area of thus prepared samples is determined. X-ray diffraction data point to the partial thermal reduction of CuFe2O4 + polymer samples. CuFe2O4 samples synthesized in the absence of polymer are reduced in the electrochemical system to form Fe–Cu composites with the different content of reduced metals depend on the temperature of thermal treatment. Electronic spectroscopy studies of samples reduced electrochemically reveal the presence of crystallites shaped as hexagonal prisms presumably formed by copper and iron-copper layers and covered by reduced iron and its oxide Fe3O4. The experiments show that the thus synthesized Fe–Cu composites exhibit electrocatalytic activity in electrochemical hydrogenation of acetophenone: its hydrogenation rate is higher by a factor of 2.5–6.4 as compared with its electrochemical reduction.