In the present research, firstly poly( vinyl alcohol)/ titanium oxide (PVA/ TiO2) nanofibers were produced from appropriate dispersions of titanium oxide nanoparticles ( with different weight percentages) in distillated water, and addition of 9wt% PVA aqeous solutions in to suspension of TiO2 by electrospinning technique. . The PVA/TiO2- based fibrous polymer electrolytes were prepared by soaking fibrous membranes in an electrolyte solution, namely, a 1M PerChlorate Lithium (LiClO4) in ethylene carbonate (EC)/dimethy carbonate (DMC) (1:1 by weight) solution, for 24 h. With increasing of the TiO2 nano¬particles to 20 wt%, the percentage of uptake of electrolytes and dimentional stability of the membranes was improved. The ionic conductivity of polymer electrolyte nano composites that prepared by electrospinning method, were measured by electrochemical impedance spectroscopy methodat 25?. The result of impedance showed that the incorporation of TiO2 into the nanofiber membrane improved the ionic conductivity from 0.7×10-5 Scm?1 to 2. 5×10-5 Scm?1 at room temperature. Cyclic voltammetry (CV) measurement of Li/PE with 20% wt. TiO2 /Li cell was performed at 25 ?C at a scan rate of 0.1Vs?1 between ?1.00 and +1.00V. The currents tend to decrease markedly during the initial cycles and stabilize afterwards. This indicates that following the initial stabilization period, the PE is able to support fully reversible process. And this polymer electrolyte has a good compatibility with the Lithium electrode. The CV of the Li/polymer electrolyte with 20% wt. TiO2/LiMn2O4 cell at room temperature was performed. The peak of anodic oxidation versus Li+/ Li was showed in 3 V. On cycling, there is no substantial change in the onodic voltages. This PE in comparision of the comertial separators used in Li-ion batteries, has a more currents and low resistant need be overcome for the cell with (PVA/TiO2)-based polymer electrolytes inorder to imped the intercalation and deintercalation of Lithium ion. The CV of the carbon/polymer electrolyte with different amount of. TiO2/LiMn2O4 cell at room temperature was performed at a scan rate of 0.1Vs?1 between 2.00 and 4.7 V. It can be observed from the cyclic voltammogram that polymer electrolytes has very good reversibility and electrochemical stability up to 4.7 V. The coefficient diffusion of Lithium ion in the (PVA/TiO2) based polymer electrolytes was evaluated by the artificial neural networks. In these polymer electrolytes, the coefficient diffusion with the increasing of the content of TiO2, was improved.