The thin films of 4% Y2O3 doped CeO2 have been deposited on different substrates of Pd film/(001) LaAlO3, Pd film/r-cut sapphire, and Pd film/Quartz using an e-beam deposition technique. The microstructures and electrical properties of the films were investigated by means of x-ray diffraction, transmission electron microscopy, and ac impedance spectroscopy. Both textured and polycrystalline films were produced on different substrates. A brick layer model was adopted to correlate the micro structure and electrical property of the films. Only the grain boundary arc was observed in the film complex impedance plots. The conductivities of the films were similar to the conductivity of 6% Y2O3 doped CeO2 bulk grain boundary because of lower preexponential factor, although the activation energies were smaller than that of bulk grain boundary. The resistive gram boundaries were found to dominate the conductivities of the films.