The electrochemical growth of dithio-oxamido copper(II) (copper rubeanate, CuRA) films onto copper electrodes was investigated by voltammetric andin situ optical reflectance techniques and the photoelectrochemical behaviour of the deposits was examined. Copper oxide-free, adherent and uniform deposits are obtained in hydroalcoholic solutions of rubeanic acid by pottential steps from −0.9 to −0.75 Vvs sce up to thicknesses of several hundred manometers. Relatively high photoreduction currents (some % monochromatic quantum yield) are obtained. The presence of copper oxides chemically grown in the CuRA matrix greatly improves both the magnitude and the stability of photoresponses.