PVA-TiO2 nanocomposite polymer electrolytes (PEs) were produced with different amounts of TiO2 (0, 5, 10, 15, and 20 wt.%) using the electrospinning process. Morphological studies of PVA-TiO2 nanofibers were accomplished with SEM. PVA-TiO2 membranes exhibited a high porosity of 79-91%. The impedance results showed that incorporation of TiO2 into the nanofiber membrane improved its ionic conductivity from 0.7 x 10(-5) to 2.5 x 10(-5) S/cm at room temperature. Nanofiber PEs showed very good reversibility and electrochemical stability up to 4.7 V. Diffusion coefficient of Li ion into PVA-TiO2 nanocomposite PEs was estimated by using a complex numerical model of partial differential equation for evaluation of ion transmission. Diffusion coefficient of PVA-TiO2 PEs containing different amounts of TiO2 (0, 5, 10, 15, and 20 wt.%) increased with increasing the nanoparticles content.