Multilayer assemblies of uniform ultrathin film electrodes with good electrical conductivity and very large surface areas were prepared for use as electrochemical capacitors. A layer-by-layer self-assembly approach was employed in an effort to improve the processability of highly conducting polyaniline (PANi) and chemically modified graphene. The electrochemical properties of the multilayer film (MF-) electrodes, including the sheet resistance, volumetric capacitance, and charge/discharge ratio, were determined by the morphological modification and the method used to reduce the graphene oxide (GO) to reduced graphene oxide (RGO) in the multilayer films. The PANi and GO concentrations could be modulated to control the morphology of the GO monolayer film in the multilayer assemblies. Optical ellipsometry was used to determine the thickness of the GO film in a single layer (1.32 nm), which agreed well with the literature value (~1.3 nm). Hydroiodic acid (HI), hydrazine, or pyrolysis were tested for the reduction of GO to RGO. HI was found to be the most efficient technique for reducing the GO to RGO in the multilayer assemblies while minimizing damage to the virgin state of the acid-doped PANi. Ultimately, the MF-electrode, which could be optimized by fine-tuning the nanostructure and selecting a suitable reduction method, exhibited an excellent volumetric capacitance, good cycling stability, and a rapid charge/discharge rate, which are required for supercapacitors. A MF-electrode composed of 15 PANi/RGO bilayers yielded a volumetric capacitance of 584 F/cm(3) at a current density of 3.0 A/cm(3). Although this value decreased exponentially as the current density increased, approaching a value of 170 F/cm(3) at 100 A/cm(3), this volumetric capacitance is one of the best yet reported for the other carbon-based materials. The intriguing features of the MF-electrodes composed of PANi/RGO multilayer films offer a new microdimensional design for high energy storage devices for use in small portable electronic devices.