Sandwiched film of MnO 2 nanosheet (MONS) and multi-walled carbon nanotube (MWCNT) was assembled by using the layer-by-layer method, based on electrostatic interaction of positively-charged poly (diallyl dimethyl ammonium chloride) and negatively-charged MONS and MWCNT. Ultraviolet–visible spectroscopy is used to probe the dynamic growth of multilayer film, exhibiting progressive enhancement of optical absorption due to the assembly of MONS and MWCNT. Thus, the assembled sandwiched film was characterized using scanning electron microscopy and X-ray photoelectron spectra. The multilayer film electrode presents excellent electrochemical capacitance properties, which were also highly dependent upon the deposition sequence and the order of structural components in sandwiched film.