Soft x-ray emission spectroscopy was used to characterize the electronic structure of seven copper nitride films, one synthesized with atomic layer deposition (ALD) and six grown with chemical vapor deposition (CVD) at different preparation temperatures. Interpretation of the x-ray emission spectra was supported by calculations of the electronic structure for bulk pure Cu(3)N and Cu(3)N with: an excess of Cu atoms, oxygen or carbon impurities, and N vacancies. The calculations are shown to describe the experimental spectra quite well. Analysis of the x-ray spectra suggests that films grown in copper rich environments and above a cut-off temperature of approximately 360 °C have a growing fraction of copper enriched areas, while films prepared below this temperature do not have these areas with excess copper.