Gel polymer electrolyte films with and without in situ TiO2 were prepared by electrospinning 16 wt.% poly(vinylidene fluoride)/poly(methyl methacrylate)-polymer solution at room temperature. Then the gel polymer electrolyte was obtained by immobilizing 1 M LiClO4-ethylene carbonate/propylene carbonate liquid electrolyte solutions in the membranes. The electrospun poly(vinylidene fluoride)/poly(methyl methacrylate) gel polymer electrolyte with 3% in situ TiO2 shows the highest ionic conductivity of 3.9 x 10(-3) S cm(-1) with electrochemical stability up to 5.1 V versus Li+/Li at room temperature. The properties of the gel polymer electrolyte prepared with in situ TiO2 were observed to be comparatively better than the one without in situ TiO2. With the superior performances, the gel polymer electrolyte prepared with in situ TiO2 is very suitable for application in Li-ion batteries. Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.