The physical and electrochemical properties of a new class of lithium ion conducting polymer electrolytes formed by dispersing nanosized Ca3(PO4)2 in the poly (vinylidene fluoride-hexafluoro propylene) (PVDF-HFP) – LiClO4 complexes have been reported. The prepared membranes were subjected to XRD, SEM, TG-DTA, and FT-IR analysis. Ionic conductivity measurements have been made as a function of temperature and lithium salt concentrations. The polymeric film with a ratio of PVDFHFP:Ca3(PO4)2:LiClO4; 75:15:10 offered maximum ionic conductivity. The interfacial property of Li/NCPE was also analyzed. The interaction that exists between the polymer and lithium salt species has been confirmed by FT-IR analysis.