We report an investigation into the distribution of copper oxidation states in oxide films formed on the surfaces of technical copper. The oxide films were grown by thermal annealing at ambient conditions and studied using Auger depth profiling and UV-Vis spectroscopy. Both Auger and UV-Vis data were evaluated applying multivariate curve resolution (MCR). Both experimental techniques revealed that the growth of Cu2O dominates the initial ca. 40 nm of oxide films grown at 175 degrees C, while further oxide growth is dominated by CuO formation. The largely coincident results from both experimental approaches demonstrates the huge benefit of the application of UV-Vis spectroscopy in combination with MCR analysis, which provides access to information on chemical state distributions without the need for destructive sample analysis. Both approaches are discussed in detail.