A new complex, tris(selenobenzoato)antimony(III) has been synthesized by a facile route and the structure determined by single crystal X-ray crystallography. The complex was used as a single source precursor to synthesize Sb2Se3 nanorods by the hot injection method whereas Sb2Se3 thin films were deposited on glass substrates by the Aerosol Assisted Chemical Vapour Deposition (AACVD) technique. The as synthesized nanorods and thin films were then characterized by powder X-ray diffraction, electron microscopy, Raman and UV/Vis spectroscopy. AACVD of the complex produced highly crystalline and pure Sb2Se3 thin films between 400 and 500 degrees C. The shape of Sb2Se3 crystallites are generally in the form of wires or thin plates, sometimes forming leaflike structures uniformly spread on the entire substrate. The size and shape of these crystallites with their stoichiometry was found to be dependent on the deposition temperature. Sb2Se3 nanorods were tested for photo electrochemical (PEC) water reduction catalysis. When simulated solar light was illuminated at the Sb2Se3/FTO surface, cathodic photocurrents were generated for H-2 generation. At open circuit potential (OCP) photo cathodic current generated with the Sb2Se3/FTO electrode was in the range of -44.8 to -52.1 mu A.cm(-2.)