Based on amine-terminated butadiene-acrylonitrile copolymer chemically crosslinked by epoxycyclohexyl polyhedral oligomeric silsesquioxane (POSS), a novel gel polymer electrolyte (GPE) were prepared by introducing one ionic liquid and LiClO4 into the polymer framework. Fourier transform infrared spectroscopy, field emission scanning electron microscopy, and X-ray diffraction analysis confirmed the interaction between the ionic liquid and LiClO4, and this interaction contributes to dissolving LiClO4 salt and increasing the ionic conductivity of GPE. Less content of POSS leads to higher ionic conductivities but lower gel content and modulus. The maximum ionic conductivity of 2.0 x 10-4 S cm-1 (30 degrees C) was achieved and an Arrhenius-type relationship between ionic conductivities and temperatures could be detected over the investigated temperature range. The generated GPE exhibited good electrochemical stability to 4 V from cyclic voltammogram tests, which made this kind of GPE a promising candidate for rechargeable lithium batteries. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012