We report the photoelectrode properties of an n-type β-Ga2O3 single crystal in aqueous solutions. The conduction and valence band-edge potentials were found to be 1.1 V higher and 2.5 V lower than the H+/H2 and O,sub>2/H2O redox potentials, respectively. Photocurrent drastically increased as photogenerated carriers were excited at a photon energy higher than the fundamental absorption edge of 4.7 eV. The incident photon-to-current conversion efficiency was 36% at 5.2 eV. Gaseous oxygen and hydrogen evolved from the photoelectrode and Pt counter electrode, respectively. The stoichiometric water splitting was demonstrated by applying an external bias of 1 V.