Highly oriented LiNbO3 thin films have been successfully synthesized by chemical solution deposition through a structure controlled metal-organic precursor. The homogeneous LiNbO3 precursor solution was prepared by controlling the reaction of metal alkoxides and selecting the ligand for modification. LiNbO3 thin films with c-axis preferred orientation were directly crystallized on sapphire C substrates from chemical solutions synthesized in this study. The epitaxial relation of LiNbO3 film to Sapphire substrate was found to depend strongly upon the precursor structure modified with beta-diketone. 1-Phenyl-1,3-butanedione (PBD) was found to be Superior to acetylacetone (acacH) and dibenzoylmethane (DBM) for the crystallization of epitaxial LiNbO3 films. The results suggested that the existence of a benzene ring in the ligand strongly influenced the degree of orientation of synthesized films. (C) 2002 Published by Elsevier Science B.V.