Graphene oxide (GO) and ruthenium polypyridyl complexes are two families of "star" materials that have been intensively studied. One of the current challenges is to fabricate their homogeneously deposited, robust composite thin films with favourable properties for practical applications. In this work, a molecular thin film was assembled with GO and a Ru(II) complex (i.e., [Ru(TTP)(2)](2+) {where TTP = 4'-(thiophen-2yl)-2,2':6',2 ''-terpyridine}) through a facile layer-by-layer self-assembly technique, and this film was studied by cyclic voltammetry, UV-visible absorption spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and photoelectrochemical measurements. The films, which were homogeneously formed by the deposition of an equal amount of GO and [Ru(TTP)(2)](2+), exhibited a well-defined surface-controlled Ru3+/Ru2+ redox couple, with both the film absorbances and peak currents linearly increasing with the deposition cycle. These films also exhibited significant cathodic photocurrent generation with, good stability and reproducibility. This layered thin film material demonstrates the potential for application in photovoltaic, energy storage, sensing and catalytic devices. (C) 2014 Elsevier Ltd. All rights reserved.