Electrochemical redox processes taking place within a hybrid polyaniline (PANI) and copper hexacyanoferrate (CuHCF) modified electrode, as well as of solution species at the surface of a modified electrode, have been investigated by near-infrared laser (785 nm) induced Raman spectroscopy. It has been shown that the composite CuHCF-PANI layers can be obtained at electrode surface by first covering the electrode by CuHCF layer using potential cycling procedure, followed by electropolymerization of aniline onto this layer at a controlled electrode potential. A reverse in this order does not result in a composite layer. Raman bands observed within a broad spectral range, as well as their dependence on electrode potential, have been analyzed. Electrochemically driven changes in spectral features related to redox transformations both of PANI and CuHCF have been observed and discussed. Slow redox transformations have been noted, most probably related to slow charge transfer within these hybrid layers. Electrochemical reduction of hydrogen peroxide at a hybrid modified electrode occurs through the redox mediation of CuHCF, whereas PANI remains not involved in this process.