Gel polymer electrolyte (GPE) is able to solve the problem of poor cyclability for high voltage cathode such as LiNi0.5Mn1.O-5(4) at elevated temperature to some extent, but the traditional GPE based on poly (vinylidene fluoride-co-hexafluoropropene) [P(VdF-HFP)] cannot meet the requirements in terms of ionic conductivity and electrochemical stability. A novel GPE, based on polyethylene-supported poly (methyl methacrylate-butyl acrylate-acrylonitrile-styrene) (P(MMA-BA-AN-St)/PE), is reported in this paper. Physical characterizations indicate that the polymer membrane has a better pore structure and higher electrolyte uptake, leading to the improved ionic conductivity of 2.7 x 10(-3) S cm(-1) at 25 degrees C for resulting GPE. Electrochemical characterizations show that the developed GPE exhibits lower interfacial resistance with lithium electrode and higher oxidative decomposition potential (up to 5.3 V, vs. Li/Li+). In addition, LiNi0.5Mn1.504 cathode shows excellent cyclic stability under 55 degrees C at 0.2C between 3 V and 4.9 V, in which the capacity retention of cathode combined with GPE is 81% after 150 cycles, compared with only 25% when using a liquid electrolyte. (C) 2016 Elsevier Ltd. All rights reserved.