Nanocrystalline thin films of copper selenide have been grown on glass and tin doped-indium oxide substrates using chemical method. At ambient temperature, golden films have been synthesized and annealed at 200 degrees C for I h and were examined for their structural, surface morphological and optical properties by means of X-ray diffraction (XRD), scanning electron microscopy and UV-vis spectrophotometry techniques, respectively. Cu2-xSe phase was confirmed by XRD pattern and spherical grains of 30 +/- 4 - 40 +/- 4 nm in size aggregated over about 130 +/- 10 nm islands were seen by SEM images. Effect of annealing on crystallinity improvement, band edge shift and photoelectrochemical performance (under 80 mW/cm(2) light intensity and in lithium iodide electrolyte) has been studied and reported. Observed p-type electrical conductivity in copper selenide thin films make it a suitable candidate for heterojunction solar cells. (c) 2006 Elsevier B.V. All rights reserved.