Porous poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP)-based polymer membranes filled with various contents of titania (TiO2) nanocrystalline particles are prepared by phase inversion technique and, along with conventional casting method for comparison. N-methyl-2-pyrrolidone (NMP) as a solvent is used to dissolve the polymer and to make the slurry with TiO2. Cast film is obtained by spreading the slurry and evaporating NMP in a dry oven, while phase inversion membrane by promptly immersing the spread slurry into flowing water as a non-solvent. Physical and electrochemical characterizations, such as morphology, thermal and crystalline behavior, and other transport properties of lithium ionic species, are carried out for the polymer films/membranes and the polymer electrolytes with absorbing an electrolyte solution. Phase inversion polymer electrolytes are proved to show superior behaviors in electrochemical properties, such as ionic conductivity, electrochemical and interfacial stability, than cast film electrolytes. This is greatly owed to highly porous structure of phase inversion membranes. Even including the feature of interfacial resistance with lithium electrode, phase inversion polymer electrolytes of PVdF-HFP/(5–20wt.% TiO2) can be optimized as the adequate ones in applying to the electrolyte medium of lithium rechargeable batteries.