Barium titanate thin films have been prepared by chemical spray pyrolysis, Aqueous spray solutions of titanium isopropoxide and barium acetate, equimolar with respect to titanium and barium, were used as precursors. Deposition was carried out at a substrate temperature of 250 degrees C, As-deposited films are amorphous. Films of BaTiO3 (perovskite) were obtained by calcination in air to 600 degrees C for various hours. Perovskite films are compact and smooth, according to their morphological aspect studied by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) combined with 4 keV Ar+ depth profiling has shown that the as-deposited film corresponds to BaTiO3 and that its composition stays constant through the whole film thickness. Residual carbon tin the form of BaCO3) coming from the organic precursor solutions is only detected at the surface of the film, limited to the first atomic monolayers as revealed by depth profiling. Calcination in air at 600 degrees C decreases this amount but BaCO3 is still present at a percentage of 25% with respect to the whole amount of Ba in the film surface. Electrical characterization of a calcined BaTiO3 film deposited on conductive n-type Si(111) was carried out with impedance spectroscopy in a frequency range of 10 Hz to 1 MHz. Assuming a film thickness of 100 nm as deduced by XPS depth profiling, the relative dielectric permittivity of our films can be estimated to be 80 at a frequency of 1 kHz. Copyright (C) 2000 John Wiley & Sons, Ltd.