For oxygen adsorbed on a Cu(OOl) surface, the O Is x-ray photoelectron intensity is found to exhibit a complex azimuthal anisotropy with an overall amplitude of ~ 26% for a grazing 10° angle of emission. No significant anisotropy is observed at 45°. Several reasons for expecting a direct relationship between such final-state scattering effects and atomic geometry are discussed, and the data are found to be suggestive of a surfacechemisorbed c(2x2) oxygen overlayer in fourfold coordination.