Polymer electrolyte composites (PECs) based on poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) that contained lithium perchlorate (LiClO4) were prepared. N-doped TiO2 (N-Ti) was used as a filler to enhance the Li+ ion conductivity. Structural modification and electrochemical properties of the PECs were investigated in order to understand the effect of N-Ti in the polymer matrix on ionic conductivity. The PECs prepared with different N-Ti contents were characterized by SEM, mapping, DSC, and a.c. impedance. From the results, the prepared N-Ti-filled PECs showed a good ability to absorb and retain the Li+ ion. The presence of N-Ti in PVDF-HFP was resulted in increasing the ion conductivity significantly. The highest ion conductivity (6.7 x 10(-4)S/cm) was observed at a relative low N-Ti content (2.5 wt.%). It is believed that the addition of N-Ti could provide the foundation for the ionic transportation and ion-mobility of the PECs and the N-doping on TiO2 led to a more enhanced ionic conductivity by higher interaction between polar groups, such as O and N of N-Ti and Li+ ions. (C) 2012 Elsevier B.V. All rights reserved.