Although micro-porous membranes made of polyethylene (PE) offer excellent mechanical strength and chemical stability, they exhibit large thermal shrinkage at high temperature, which causes a short circuit between positive and negative electrodes in cases of unusual heat generation. We tried to develop a new technology to reduce the thermal shrinkage of PE separators by introducing γ-Al2O3 particles treated with coupling agent on PE separators. Nanocomposite γ-Al2O3/PE separators were prepared by the dip coating of polyethylene(PE) separators in γ-Al2O3/poly(vinylidenefluoride-hexafluoropropylene) (PVDF-HFP)/crosslinker (1,3,5-trially-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TTT) solution with humidity control followed by electron beam irradiation. γ-Al2O3/PVDF-HFP/TTT (95/5/2)-coated PE separator showed the highest electrolyte uptake (157%) and ionic conductivity (1.3mS/cm). On the basis of the thermal shrinkage test, the nanocomposite γ-Al2O3/PE separators containing TTT irradiated by electron beam exhibited a higher thermal resistance. Moreover, a linear sweep voltammetry test showed that the irradiated nanocomposite γ-Al2O3/PE separators have electrochemical stabilities of up to 5.0V. In a battery performance test, the coin cell assembled with γ-Al2O3/PVDF-HFP/TTT-coated PE separator showed excellent discharge cycle performance.