A monolayer of a ferrocenyl hemicyanine was covalently self-assembled on an indium tin oxide (ITO)-coated glass substrate, and was characterized by UV/Vis absorption and X-ray photoelectron spectroscopy, and cyclic voltammetry. The photoelectrochemical properties and mechanism of photocurrent generation have also been studied. This monolayer film was found to exhibit a large anodic photocurrent density of 0.13 microA/cm2 with the highest photoelectric yield of 3.32% under irradiation of white light (730 nm > lambda > 325 nm) at a bias potential of +0.4 V versus saturated calomel electrode.