A method for the controlled self-assembly of nanoscale ferrocyanides of transition metals MFeCN, such as cobalt (CoFeCN), nickel (NiFeCN) and copper (CuFeCN), in the role of cathode materials by layer-by-layer synthesis (LbL) on a conducting support was proposed. The structure and morphology of the compounds were studied by X-ray diffraction analysis, scanning electron microscopy with energy dispersive X-Ray analysis (EDX) and ATR-FTIR analysis. The effect of synthesis conditions (precursor of transition metals, number of cycles of layer deposition) on the particle morphology and the quality of the films obtained was shown. The electrochemical behavior of cathode materials was studied in a solution of magnesium salt by cyclic voltammetry. On an example nickel ferrocyanide was proved that the synthesis method used allows controlling the self-assembly of cathode materials based on ferrocyanides of transition metals.