(100-x) LiCF3SO3 + (x) CeO2 composite electrolytes were prepared using sol-gel technique followed by sintering at 300 °C for four hours. Structural property and conductivity of the prepared composite electrolytes were studied using X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray (EDX) analysis and Impedance Spectroscopy. The XRD spectra show only crystalline peaks of CeO2 indicating that LiCF3SO3 exists in the form of amorphous phase. This is confirmed by SEM and EDX analyses. The highest ionic conductivity at room temperature is found to be in the order of 10-3 S cm-1 for the composite of 70 mol % LiCF3SO3 - 30 mol % CeO2. The conductivity of the composite electrolytes is observed to increase gradually with temperature.