Zirconium–stannate titanate Zr1−xSnxTiO4 (ZTS) thin films, undoped and doped with Sb, Ta and Nb, were prepared by a polymeric precursor technique. The ZTS films were deposited on the multilayered substrates (Pt/Ti/SiO2/Si) by means of multiple spin-coating. After this deposition, the samples were heated at different temperatures (300–700°C). The chemical composition of these films and bulk ZTS samples was investigated by using x-ray photoelectron spectroscopy and selected-area XPS depth profiling. A partial surface segregation of SnIV and the presence of Sn0, TiII and TiIII species in the films were revealed from XPS depth profiles. An optimized ZTS deposition process, where an oxidizing agent (H2O2) is added to the gel, is proposed. Copyright © 2002 John Wiley & Sons, Ltd.