Nanoscale TiO2 particle filled poly(vinylidenefluoride-co-hexafluoropropylene) film is characterized by investigating some properties such as surface morphology, thermal and crystalline properties, swelling behavior after absorbing electrolyte solution, chemical and electrochemical stabilities, ionic conductivity, and compatibility with lithium electrode. Decent self-supporting polymer electrolyte film can be obtained at the range of <50 wt% TiO2. Different optimal TiO2 contents showing maximum liquid uptake may exist by adopting other electrolyte solution. Room temperature ionic conductivity of the polymer electrolyte placed surely on the region of > 10(-3) S/cm, and thus the film is very applicable to rechargeable lithium batteries. An emphasis is also be paid on that much lower interfacial resistance between the polymer electrolyte and lithium metal electrode can be obtained by the solid-solvent role of nanoscale TiO2 filler.