Thin films of LiNbO3 Were fabricated on sapphire(012), MgO(001), and Si(111) substrates by the sol-gel process. Under optimized conditions, films deposited onto sapphire(012) were epitaxially grown. Preferred orientations, however, were not observed in the films on MgO(001) and Si(111) by x-ray diffraction measurements. Morphology of the epitaxial films on sapphire(012) was examined by scanning electron microscopy, which indicated that the films were smooth and had a pore-free surface. Electrical and optical measurements on the epitaxial films revealed that the properties of the films were very similar to those of the single crystalline LiNbO3, while films deposited onto Si(111) did not.show any orientational behaviors. The highest quality films with epitaxy were obtained only on sapphire(012). The remaining substrates appeared to be not suitable for growing epitaxial LiNbO3 films by the sol-gel method.