Acrylonitrile-sodium styrene sulfonate copolymer/layered double hydroxides nanocomposites were prepared by in situ aqueous precipitation copolymerization of acrylonitrile (AN) and sodium styrene sulfonate (SSS) in the presence of 4-vinylbenzene sulfonate intercalated layered double hydroxides (MgAl-VBS LDHs) and transferred to acrylonitrile-styrene sulfonic acid (AN-SSA) copolymer/LDHs nanocomposites as a proton-conducting polymer electrolyte. MgAl-VBS LDHs were prepared by a coprecipitation method, and the structure and composition of MgAl-VBS LDHs were determined by X-ray diffraction (XRD), infrared spectroscopy, and elemental analysis. X-ray diffraction result of AN-SSS copolymer/LDHs nanocomposites indicated that the LDHs layers were well dispersed in the AN-SSS copolymer matrix. All the AN-SSS copolymer/LDHs nanocomposites showed significant enhancement of the decomposition temperatures compared with the pristine AN-SSS copolymer, as identified by the thermogravimetric analysis. The methanol crossover was decreased and the proton conductivity was highly enhanced for the AN-SSA copolymer/LDHs nanocomposite electrolyte systems. In the case of the nanocomposite electrolyte containing 2% (by mass) LDHs, the proton conductivity of 2.60x10(-3) S.m(-1) was achieved for the polymer electrolyte.