This paper deals with a simple and low-cost method developed to deposit hematite (alpha-Fe(2)O(3)) layers on a fluorine-doped tin oxide (FTO/F center dot SnO(2)) substrate by thermal decomposition of solid iron(III) chloride hexahydrate (FeCl(3) 6H(2)O) Deposition procedure takes place through chemical intermediate iron(III) oxide chloride (FeOCl) film. A crucial influence of atmosphere dynamics involved in the calcination process of FeOCl has been observed As-deposited films were characterized by means of Conversion Electron Mossbauer Spectroscopy (CEMS), Grazing Angle X-Ray Diffractometry (GAXRD), Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) analysis Final nanocrystalline hematite film with a cactus-field-like design consists of 20 nm thick porous crystal plates. A process of hematite doping by tin atoms from substrate coating is also discussed (C) 2010 Elsevier B V. All rights reserved.