Photoelectrochemical assemblies consisting of gold nanoparticles and a tris(2,2'-bipyridine)ruthenium(II)-viologen linked disulfide derivative ([RuVS](2)) were constructed on gold electrodes, by a combination of salting-out and self-assembly processes. Structural characterization of the nanostructured assemblies was carried out by scanning electron microscopy and cyclic voltammetry. The adsorbed amount of the tris(2,2'-bipyridine)ruthenium(II)-viologen linked moiety (RuVS) was fairly well correlated with the ratio of the total gold surface area of the nanostructured electrode. Nanostructured assemblies consisting of similar to 50 to similar to < 100 nm particles showed high photocurrent efficiencies. (C) 2003 Elsevier B.V. All rights reserved.