A series of novel nano-composite polymer electrolytes (NCPEs) are prepared with the ionic liquid of N-methyl-Nmethoxyethylpiperidiniumbis(trifluoromethanesulfonyl)imide (PP1201TFSI) as plasticizer and nano-sized TiO2 as additive. The effect of the ratio of TiO2 to Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) on the properties of the NCPEs are studied, such as the crystallinity and ionic conductivity. The results indicate that the nano-composite polymer electrolyte NCPE-2, that the ratio of TiO2 to PVDF-HFP is 10%, exhibits the highest ionic conductivity of 2 x10(-3) S.cm(-1) with the lowest crystallinity. The LiFePO4/NCPE-2/Li coin-typed cell cycled at 0.5 C shows the 1st discharge capacity of 127.9 mAh g(-1) and remains 97.6% of the initial discharge capacity on the 50th cycle. (C) 2016 Elsevier B.V. All rights reserved.