A novel non-woven fabric supported polymer membrane based on poly(methyl methacrylate-polyhedral oligomeric silsesquioxane) (P(MMA-POSS)) copolymer is prepared by phase inversion method. The difficulty in preparing PMMA membrane by phase inversion method is solved. Further, the P(MMA-POSS) based gel polymer electrolyte (GPE) is prepared by absorbing liquid electrolyte. The morphology structure and properties of the P (MMA-POSS) membrane and electrochemical performance of P(MMA-POSS) GPE are investigated. The results of the analysis exhibit that the P(MMA-POSS) membrane possesses a significant pore structure, and P(MMA-POSS) membrane containing 10 wt% POSS in polymerization presents the optimal electrolyte uptake of 275 wt%. Compared with pure PMMA GPE without introducing POSS, the excellent electrochemical performances of P (MMA-POSS) GPE are demonstrated: a higher ionic conductivity of 3.41 mS cm(-1) at room temperature, a wider electrochemical stability window of 5.01 V (vs. Li/Li+), the excellent interface compatibility with anode and a satisfactory lithium ion transference number of 0.49. The lithium ion battery with the P(MMA-POSS) GPE also exhibits a higher charge-discharge capacity of 151.9 mAh g(-1) at 0.2 C, and a capacity retention rate of 99.8% at 0.5 C is confirmed after 100 cycles.