X-ray photoelectron spectroscopy (XPS) spectra are presented, which are obtained from an oxygen-free single crystalline (sc-) titanium nitride (TiN) sample. The investigated film has been grown on a magnesium oxide (MgO) single crystal with the (001) orientation. Unbalanced Reactive Magnetron Sputter deposition was used to deposit the TiN film in an argon/nitrogen atmosphere at 5 × 10−3 mbar and a temperature of 800 °C. The sample has been transferred in situ from the deposition chamber to the XPS device in order to prevent surface oxidation of the sample. Atomic force microscopy (AFM), X-ray diffraction (XRD), Rutherford backscattering (RBS) and angle resolved (AR-) XPS have been used to characterize the sample in detail. This work is dedicated to the XPS characterization of a representative oxygen-free sc-TiN sample. Detailed scans are presented and discussed for the Ti 2p, O 1s, N 1s, Ti 2s, valence band and Ti LMM regions. The spectra contain shake-ups, surface and bulk plasmons, that can be separated and quantified by the presented evaluation procedure.