There have been many studies aimed at improving the ionic conductivity of solid polymer electrolytes (SPEs). Nevertheless, no reports in the literatures can be found on the combined effect of inner-structure of polymer and nano-fillers. In this work, Novel anionic composite gel polymer electrolytes poly (vinyl alcohol)/poly (methyl acrylate-co-sulfonate allyloxy PVA/P (MA-co-AHPS) (PVMS) and series of composite polymer electrolytes PVA/P (MA-co-AHPS)-x wt.% Al2O3 (PVMS-Alx) have been prepared by blending and chemical copolymerization. The physicochemical properties of these polymer electrolytes have been studied in detail by FTIR, TG, SEM and AC analyses. Moreover, maximum conductivity value (1.08 x 10(-3) S cm(-1)) has been achieved by optimizing the inner-structure of the polymer and the content of ceramic filler. The ionic conductivity is found to be greatly dependent on the special spherical structure, anionic emulsion sodium sulfonate allyloxy (AHPS) and nano-sized alumina filler (Al2O3), which can guarantee wider electrochemical window, higher discharge capacity, better interface stability and more excellent cycling performance. (C) 2014 Elsevier B.V. All rights reserved.