Multilayered polyelectrolyte membrane was prepared by layer by layer (LbL) method by alternating deposition of poly (diallyl dimethyl ammonium chloride) (PDDA) and an anionic polyelectrolyte chosen from graphene oxide (GO), sulfonated GO (sGO), or sulfonated poly (phenylene oxide) (sPPO). LbL deposited bilayers of {PDDA / GO}(n) and {PDDA / sGO}(n) were prepared and their accumulation behaviors were studied. After the LbL assembly of the above polyelectrolyte tetra-layers of {PDDA / GO (or sGO) / PDDA / sPPO}(n) onto the Nafion film, the adaptability as a membrane for direct methanol fuel cell (DMFC) was investigated in terms of proton conductivity and methanol permeability