The structures and the electronic states in electrodeposited semiconductor Cu -O thin films have been investigated for each annealing temperature (T A ) by X-ray diffraction (XD) and X-ray absorption spectroscopy (XAS) near the Cu K edge using synchrotron radiation. The thin films prepared as grown and annealed at T A ≤ 175 °C, 200 °C ≤ T A ≤ 300 °C, T A = 400 °C are characterized mainly by the pure Cu 2 O-type structure, the pseudo-Cu 2 O-type having a superlattice structure, and two phases of Cu 2 O-type and CuOtype structures, respectively, while the film annealed at T A = 500 °C is single-phase CuO-type. The XAS spectra suggest that there is a structural phase transition occurring at about 400 °C, which induces a modulation of the local structure around Cu ions observed in the extended X-ray absorption fine structure (EXAFS) and the occupational electronic band states of Cu-4p localized just above the Fermi level, taken from X-ray absorption near edge structure (XANES). The open-circuit voltage suggests that the photosensitivity of the Cu -O thin films strongly depends on the annealing treatment and shows a crossover from an n-type to a p-type semiconductor.