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In this paper,we developed new composites electrolyte based on poly (butyl methacrylate-styrene) (P(BMA-St)).The copolymer P(BMA-St) was synthesized by emulsion polymerization and the copolymer membrane was prepared through phase inversion by hybrid nano-sized fumed silica.The structure and the performance of the copolymer,the membrane and the GPE were characterized by FTIR,GPC,SEM,XRD,DSC/TG,LSV,CA,and EIS.It is found that the copolymer has low crystallinity and is formed through the breaking of double bond C=C in each monomer.When doped 10 % fumed silica,the membrane has lower glass transition temperature but higher thermal stability and its mechanical strength is improved compared to P(BMA-St).The composites electrolyte is electrochemically stable up to 5.2 V (vs.Li/Li+) and its conductivity is 3.52×10-3 S·cm-1 at ambient temperature.