Typical characteristics of BaTiO3 thin films, such as hysterisis behavior, spontaneous polarization below the Curie temperature, faster switching speed etc., are particularly of much attention for high capacitance integrated elements, dynamic random access memories (DRAMs), phase conjugation, holographic optical data storage, two-beam coupling and optical computing. Several techniques have been employed for the fabrication process of such ferroelectric thin films. Among other methods, Sol-Gel and MOD prove to be a powerful and inexpensive means to deposit thin films. The main advantages of these deposition techniques are good homogeneity, ability to precisely control the stoichiometry of the film, lower temperature processing, and the ability to produce high-purity materials for electronics and optics without much investment in equipment. We report the structural characterization of BaTiO3 films deposited on single crystal Si (100) and MgO (100) substrates by sol-gel process. The films were prepared by the sol-gel process and annealed at different temperatures. In this method the sol-gel polymerization is initiated by adding water to a solution of alkoxide in methanol. The chemical conditions are generally chosen in such a way that nearly complete hydrolysis occurs. A series of experiments ranging from X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), were conducted on the spin-coated films and their correspondingly annealed films at different temperatures.