Composite nanostructures of tungsten oxide and polyaniline (PANI) were fabricated on carbon electrode by electrocodeposition using sodium dodecylbenzene sulfonate (SDBS) as the template. The morphology of the composite can be controlled by changing SDBS surfactant and aniline monomer concentrations in solution. With increasing concentration of aniline in surfactant solution, the morphological change from nanoparticles to nanofibers was observed. The nanostructured WO3/PANI composite exhibited enhanced capacitive charge storage with the specific capacitance of 201 F g−1 at 1.28 mA cm−2 in large potential window of -0.5~ 0.65 V versus SCE compared to the bulk composite film. The capacitance retained about 78% when the sweeping potential rate increased from 10 to 150 mV/s.