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Hyperbrandched poly(amine-ester)(HBPAE) grafted nano-silica (SiO2-g-HBPAE) was made and applied to the polymer electrolyte in this paper.A novel Quasi-solid state polymer composite electrolyte based on hyperbranched poly(amine-ester) incorporating hypergrafted nano-silica (SiO2-g-HBPAE) doped with lithium salts was fabricated: SiO2-g-HBPAE/HBPAE/LiClO4.The AB2 monomer was firstly synthesized through Michael-addition reaction and then self-condensation on the surface of nano-silica pretreated by KH550 and MMA.Fluorescence intensity increased along with the reaction indicated that AB2 monomer and SiO2-g-HBPAE/HBPAE was successfully prepared.X-ray photoelectron spectroscopy(XPS) characterization indicated hyperbranched poly(amine-ester) had been successfully densely grafted to nano-silica surface.Transmission electron microscope(TEM) and Static light scattering(SLLS) measurement showed that SiO2-g-HBPAE had a thickness of 50nm corona with SiO2 as core in solid state and a diameter of 180-320nm in DMF solution depending on the content of nano-silica during the grafting,and the grafting ratio was almost 283.1% indicated by Thermo gravimetric analysis(TGA).Incorporating nano-silica to HBPAE could not only decrease the glass transition temperature according to the Differential scanning calorimetry(DSC) characterization,but also increase the elastic modules and viscosity modules shown by Rheological measurement results.When 50wt%LiClO4 was doped,the conductivity of SiO2-g-HBPAE/ HBPAE reached 1.4 × 10-5S/cm at 30℃ and 10-3S/cm at 100℃.