Size-dependent electronic structures around the Fermi level of glutathione-protected gold clusters (0.9-1.4 nm in core diameter) were analyzed on the basis of photoinduced charge separation at the interface between the gold cluster and TiO(2). Electron levels such as HOMO and LUMO were estimated from the dependencies of the photocurrents on the irradiation wavelength and the standard electrode potentials of electron donors employed. The potential of the occupied levels involved in the charge separation under visible or near infrared light shifts negatively as the cluster size increases.