Photoelectron spectra of a Si wafer, on which copper phthalocyanine was evaporated with a thickness of 50 A˚, were measured using grazing incidence x rays under a total reflection condition. It was observed that the backgrounds owing to inelastic electron scattering in solids were reduced. It was also observed that the substrate Si signal was removed and that surface signal was enhanced due to the total x‐ray reflection. Oxygen depth was determined using the angle dependence of the x‐ray photoelectron spectral intensity. ©1995 American Institute of Physics.