The multilayer films consisting of graphene oxide and a cobalt complex were fabricated though electrostatic layer-by-layer self-assembly technique and characterized by UV-Vis absorption spectroscopy, Xray photoelectron spectroscopy, scanning electron microscopy, and cyclic voltammetry. The results demonstrated that the hybrid films were successfully prepared and exhibited good electrochemical activity. The film was also subjected to photoelectrochemical studies and were found to exhibit large cathodic photocurrent density of 6.1 mu A/cm(2) while irradiated with 100 mW/cm(2) polychromatic light (730 nm > lambda > 325 nm) at an applied potential of -0.4 V versus saturated calomel electrode. (C) 2013 Elsevier Inc. All rights reserved.