Abstract: In order to solve the security problems of the lithium-ion batteries,a nano-SiO₂/poly(vinylidene fluoride-co-hexafluoro-propylene) (PVDF-HFP) gel polymer electrolyte with high ionic conductivity was prepared,using nano-SiO₂ as an additive,LiClO₄ as the salt,and propylene carbonate (PC) and dimethyl carbonate (DMC) as the plasticizer. The structure and microstructure were characterized using XRD,the ionic conductivity was determined by AC impedance method,the electrochemical stability was measured by linear scan voltammetry experiment,and the charge-discharge of the polymer lithium batteries based on this composite gel polymer electrolyte was investigated. The results indicate that the highest conductivity of the gel polymer electrolyte is 7. 56 ×10^-3 S/ cm at 20℃,and the electrochemical character of the gel polymer electrolyte is stable under 4. 6 V,and the polymer lithium batteries have excellent electrochemical performances. The SiO₂/LiClO₄/PVDF-HFP composite gel polymer electrolyte shows the potential application in lithium ion batteries.