Microstructured composite films based on poly(3,4-ethylenedioxythiophene) (PEDOT) and nanographene oxide (nGO) were prepared by electrochemical polymerization of 3,4-ethylenedioxythiophene in nGO aqueous solution on the surface of glassy carbon electrodes at a constant potential. The microstructure pattern of the electropolymerized films was shaped using microsphere lithography process with mono- or bilayers of polystyrene microspheres arranged on the electrode surface. During the electropolymerization, the nGO was incorporated into the composite film as a charge-compensating anion for PEDOT accelerating the electropolymerization process. We demonstrate that addition of small amount of sodium dodecyl sulfate to the reaction medium suppresses the aggregation of the nGO sheets resulting in a better defined defect-free morphology of the PEDOT:nGO films. After dissolving the template polystyrene particles, PEDOT:nGO films retained a porous honeycomb-like structure. The nGO incorporated into PEDOT:nGO composite was electrochemically converted to reduced nGO (nRGO) in a simple one-step reduction process. We show in this paper that the resulting PEDOT:nRGO films demonstrate increased redox capacitance and enhanced electroactivity for ascorbic acid oxidation.