We report the self-buckling (or peeling off) of cubic Cu3N films deposited by DC magnetron sputtering of a Cu target in a nitrogen environment at a gas pressure of 1 Pa. The deposited layer partially peels off as it is exposed to ambient air at atmospheric pressure, but still adheres to the substrate. The chemical composition of the thin film as investigated by means of X-ray photoelectron spectroscopy (XPS) shows a considerable surface oxidation after exposure to ambient air. Grazing incidence X-ray diffraction (GIXRD) confirms the formation of a crystalline Cu3N phase of the quenched film. Notable are the peak shifts in the deposited film to smaller angles in comparison to stress-free reference material. The X-ray pattern of Cu3N exhibits clear differences in the integral width of the line profiles. Changes in the film microstructure are revealed by X-ray diffraction, making use of X-ray line broadening (Williamson–Hall and Stokes–Fourier/Warren–Averbach method); it indicates that the crystallites are anisotropic in shape and show remarkable stress and micro-strain.