Next generations electrochemical energy storage devices require high-power, high-energy density, simultaneously. To achieve this goal, it is essential to identify novel electrode materials based on nanoparticles, nanotubes or nanofibers with decreased transport length of ions/electrons and high surface area. Nanomaterials such as carbon nanotubes and conducting polymeric nanofibers /nanoparticles with their exotic properties can significantly increase power (W/kg) and energy density (Wh/kg) in addition, to their longer life cycles and charging-discharging efficiency. We assembled free-standing multilayered thick (10 to 60 microns) electrodes of conducting polyaniline (PANi) and multiwalled carbon nanotubes (MWNTs) that are robust, binder-free using rapid spray and vacuum-assisted layer by layer techniques. The electrode microstructure reveals porous nanostructure with high surface area; Preliminary results for these highly conductive electrodes (4.4 S/cm) show high pseudocapacitance of 210 F/cm3 and are stable over 1000 cycles. We will present our findings on the optimization of the free standing asymmetric electrode morphology and electrochemical performance in aqueous and organic electrolytes.