Nano-SiO2 as dopant was used for preparing polyethylene-supported poly(methyl methacrylate-co-butyl acrylate) (P(MMA-co-BA)/PE) based membrane and corresponding gel polymer electrolyte (GPE), which is applied to improve the cyclic stability of high voltage lithium ion battery. P(MMA-co-BA)/nano-SiO2/PE based membranes and corresponding GPEs were characterized with scanning electron spectroscopy, X-ray diffraction, electrochemical impedance spectroscopy, mechanical test, thermogravimetric analysis, linear sweep voltammetry, and charge/discharge test. It is found that the GPE with 5wt.% nano-SiO2 shows the best performance. Compared to the undoped membrane, the 5wt.% nano-SiO2 doped membrane has a better pore structure and higher electrolyte uptake, leading to the enhancement in ionic conductivity of the resulting GPE from 1.23×10−3 to 2.26×10−3 S.cm−1 at room temperature. Furthermore, the thermal stability of the doped membrane is increased from 300 to 320°C while its decomposition potential of GPE is from 5.0 to 5.6V (vs. Li/Li+). The cyclic stability of Li/GPE/Li(Li0.13Ni0.30Mn0.57)O2 cell at the high voltage range of 3.5V ∼ 5.0V is consequently improved, the capacity retention of the cell using the doped membrane is 92.8% after 50 cycles while only 88.9% for the cell using undoped membrane and 66.9% for the cell using liquid electrolyte.