Three-dimensional multistructure assemblies consisting of gold nanoparticles and a sulfur-containing ruthenium (II) tris(2,2-bipyridine) derivative were fabricated on an ITO electrode by their alternate self-assembling. Absorption spectra of the assemblies showed immobilization of the gold surface and the ruthenium complex. Broadening and red shift of the plasmon band were observed by increasing the number of assembled layers, which revealed the presence of interparticle plasmon coupling. In the presence of triethanolamine as a sacrificial reducing agent, photocurrent responses from the multistructure assemblies were clearly observed in the anodic direction. The photocurrent increased with increasing the number of assembled layers.