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Studies were carry out to obtain an electrode material with developed surface and expressed electroactivity by synthesis of composite materials based on reduced graphene oxide (RGO) and poly-o-phenylenediamine (PPD). To this end, two-step graphene oxide (GO) reduction including chemical (in the water solution of ascorbic acid) and electrochemical (via cyclic voltammetry in 0.1 M NaClO4 water solution) steps was proposed. The extent of GO reduction was controlled by the IR spectra. It was shown that separately chemical or electrochemical reduction of GO is not sufficient. Various methods were studied to modify an electrode surface with a composite material – synthesis of PPD on the RGO surface and reduction of GO, deposited on the PPD from its suspension. The electrical capacity of RGO-PPD composite was shown to exceed that of pure PPD, while composite films show expressed redox activity due to the presence of PPD. AFM image of RGO film prepared by electrochemical reduction of GO on ITO-coated glass electrode in 1M H2SO4 was obtained. Also the method of coating the electrode by the reduced graphene oxide ( RGO ) in thinlayer cell was developed. It was shown that in this case composite RGO-PPD films reveal the developed surface due to nanosheets of RGO, and pronounced redox activity due to the presence of PPD . Creation of such materials will further find applications in various energy storage devices, corrosion-proof coatings, and sensors of any kind. Furthermore, in some cases the presence of an electroactive polymer may enhance adhesion to the substrate material. A sufficiently high stability of PPD in a wide potential range either outside or inside an RGO composite may substantially widen the application field of such a material.