Thin films of delafossite of CuAlO2 laminar crystals on metal substrates (Ni plates) were prepared by sol-gel processing and subsequent thermal treatment in vacuum. The influence of annealing treatment on surface morphologies and structure of the samples is discussed. Field-emission scanning electron microscope (FESEM) shows the laminar surface architecture of the as-prepared CuAlO2 thin films. The electrical property of sample was investigated by current-voltage analysis, which indicates that a rectifying junction between CuAlO2 film and metal substrate is formed and forward current exceeds reverse current by a factor of up to three. Otherwise, the photoelectrochemical characteristics recorded under 250mW/cm(2) illumination show that the as-prepared thin film electrode which was annealed at 1150 degrees C for 4 h in vacuum possesses the highest photocurrent density, which is 0.7mA/cm(2) at 0V vs Ag/AgCl. (C) 2010 Elsevier B.V. All rights reserved.