Composite polymer electrolytes based on poly(ethylene glycol) (PEG), magnesium acetate [Mg(CH3COO)2], and x wt% of cerium oxide (CeO2) ceramic fillers (where x = 0, 5, 10, 15 and 20, respectively) have been prepared using solution casting technique. X-ray diffraction patterns of PEG–Mg(CH3COO)2 with CeO 2 ceramic filler indicated the decrease in the degree of crystallinity with increasing concentration of the filler. DSC measurements of PEG–Mg(CH3COO)2–CeO2 composite polymer electrolyte system showed that the melting temperature is shifted towards the lower temperature with increase of the filler concentration. The conductivity results indicate that the incorporation of ceramic filler up to a certain concentration (i.e. 15 wt%) increases the ionic conductivity and upon further addition the conductivity decreases. The transference number data indicated the dominance of ion-type charge transport in these specimens. Using this (PEG–Mg(CH3COO)2–CeO2) (85-15-15) electrolyte, solid-state electrochemical cell was fabricated and their discharge profiles were studied under a constant load of 100 kΩ.