Nano ZnO with an average size of 8 nm was prepared by thermal decomposition of zinc oxalate at 450 °C. A series of based composite polymer electrolyte PEO-LiClO4 and nano ZnO as a filler have been synthesized using solution cast technique, with varying the filler ratio systematically. XRD, DSC and FTIR studies have been conducted to investigate the structure and interaction of different groups in the composite polymer electrolyte. Effect of nano ZnO ceramic filler concentration on the structure of composites and their electrical properties (DC-conductivity, AC-conductivity, dielectric constant, dielectric loss and impedance) at different frequencies and temperatures was studied. Melting temperature (Tm) of PEO decreased with the addition of both LiClO4 salt and nano ZnO filler due to increasing the amorphous state of polymer. All composite samples showed an ionic conductivity. The maximum room temperature ionic conductivity is found for (ZnO)0.5(PEO)12(LiClO4) composite sample. All the results are correlated and discussed.