The effect of low molecular weight borate ester on the ionic conductivity of polyacrylonitrile (PAN) was systematically investigated by means of measuring conductivity using the impedance technique. Gel polymer electrolyte (SPE) films consisting of PAN as host polymer, LiCF3SO3 and LiBF4 as ionic salts, and poly (ethylene glycol) borate ester (PEGB), ethylene carbonate/propylene carbonate (EC/PC) as plasticizers were prepared by physical blending method. All measurements were performed on electrolyte samples with various contents. Fourier transform infrared spectroscopy (FT-IR) gave evidence of the interactions among PAN, plasticizers and lithium salt. The surface morphology of the electrolytes was investigated by scanning electron microscopy (SEM). Thermal properties of these materials were searched with thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Conductivity studies of these blend polymer electrolytes were carried out in the temperature range 20–100°C. The maximum ionic conductivity values of 1.8×10−3 and 1.4×10−4 Scm−1 were measured for the film containing 4PAN-10EC/PC-4LiBF4 and 4PAN-10PEGB-4LiCF3SO3, respectively, at room temperature. These films have a good conductivity, better dimensional stability and wide electrochemical stability window. These unique properties make the composite gel membranes suitable for application as electrolyte in rechargeable Li-ion batteries.