We present results from X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) of oxidized polycrystalline copper surfaces [Cu(I) and Cu(II), respectively] exposed to a 1.0 mM aqueous solution of Na2S (sodium sulfide) for several hours. Scanning electron microscopy reveals that the Cu oxide surfaces attain a much rougher texture upon sodium sulfide exposure, and that the exposed Cu(II) oxide sample exhibits areas with crystallites. The XAS spectra show that sodium sulfide effectively reduces Cu(II) oxide to Cu(I) compounds. The RIXS spectra of the exposed surfaces closely resemble those of the Cu2O reference sample with the notable exception of their Cu L-III,L-II-RIXS spectra. We conclude that copper evidently forms a Cu(I) compound with oxygen but with a Cu 3d-band of much reduced width, pointing to the possibility of a more complex compound containing both oxygen and sulfur. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3504891] All rights reserved.