A novel kind of sandwiched polymer membrane was prepared, which consists of two outer layers of electrospun poly(vinyl difluoride) (PVDF) fibrous films and one inner layer of poly(methyl methacrylate) (PMMA) film. Its characteristics were investigated by scanning electron microscopy and X-ray diffraction. The membrane can easily absorb non-aqueous electrolyte to form gelled polymer electrolytes (GPEs). The resulting gelled polymer electrolytes had a high ionic conductivity up to 1.93 x 10(-3) S cm(-1) at room temperature, and exhibited a high electrochemical stability potential of 4.5 V (vs. Li/Li+). It is of great potential application in polymer lithium-ion batteries. (c) 2008 Elsevier B.V. All rights reserved.