Novel well-defined cuprous oxide (Cu2O) thin films are synthesized on indium-doped tin oxide (ITO) covered glass substrates by electrochemical deposition, with cationic surfactant, cetyl trimethylammonium bromide (CTAB) as shape controlled agent. The effects of the quantity of CTAB, the temperature and concentration of electrolyte were studied. It was shown that the morphology evolved from flower-leaves to spheres with increasing quantity of CTAB, which indicated that the morphology varied with the CTAB concentration. Furthermore, the optical properties of Cu2O films was investigated and found that Cu2O film composed of shagginess spheres have better photoluminescence (PL) properties. Also, the Cu2O film can be used as substrates for functional applications. (c) 2007 Elsevier B.V. All rights reserved.