The possibility of using silicon as the substrate electrode for the deposition of electroactive films of transition metal hexacyanoferrates was investigated. The silicon surface was successfully modified by the electroactive films based on a simple method. The studies of the electrochemical behavior and electrocatalytic properties of a palladium hexacyanoferrate (PdHCF) film-modified silicon electrode showed that the electrode fabricated had excellent properties and electrochemical activity. The possibility of the use of silicon substrate was also examined for the deposition of NiHCF and CoHCF films. The modification was carried out by electrodeposition of metals onto the substrate surface and chemical transformation of the metallic films deposited into their hexacyanoferrate salts. The results obtained from electrochemical studies indicate clearly that the electroactive films have excellent electrochemical activities compared with conventional hexacyanoferrate-based modified electrodes. In addition, deposition of electroactive films onto silicon surface provides an enhanced stability of the electroactive films during potential cycling and long-term storage.