Cuprous oxide and copper thin films were potentiostatically electrodeposited in an acetate bath. Voltammetric curves were used to investigate the growth parameters; deposition potential, pH and temperature of the bath. Deposition potential dependency on the structural, morphological, optical and electronic properties of the films were investigated by the X-ray diffraction measurements, scanning electron micrographs, absorption measurements and dark and light current-voltage characterisations. It was observed that single phase polycrystalline Cu2O can be deposited from 0 to -300 mV Vs saturated calomel electrode (SCE) and co-deposition of Cu and Cu2O starts at -400 mV Vs SCE. Further increase in deposition potential from -700 mV Vs SCE produces single phase Cu thin films. Single phase polycrystalline Cu2O thin films with cubic grains of 1-2 mu m can be possible within the very narrow potential domain around -200 mV Vs SCE. Enhanced photoresponse in a photoelectrochemical cell is produced by the Cu2O thin film prepared at -400 mV Vs SCE, where Cu is co-deposited with Cu2O with random distribution of Cu spheres on the Cu2O surface. This study reveals that a single deposition bath can be used to deposit both Cu and Cu2O separately and an admixture of Cu-Cu2O by controlling the deposition parameters. (c) 2005 Elsevier B.V. All rights reserved.