The nitrogen doping of titanium dioxide nanotubes (TiO₂ NTs) was investigated as a result of well-controlled plasma nitriding of TiO₂ NTs at a low temperature. This way of nitrogen doping is proposed as an alternative to chemical/electrochemical methods. The plasma nitriding process was performed in a preparation chamber connected to an X-ray photoelectron spectroscopy (XPS) spectrometer, and the nitrogen-doped TiO₂ NTs were next investigated in situ by XPS in the same ultrahigh vacuum (UHV) system. The collected high-resolution (HR) XPS spectra of N 1s, Ti 2p, O 1s, C 1s, and valence band (VB) revealed the formation of chemical bonds between titanium, nitrogen, and oxygen atoms as substitutional or interstitial species. Moreover, the results provided a characterization of the electronic states of N–TiO₂ NTs generated by various plasma nitriding and annealing treatments. The VB XPS spectrum showed a reduction in the TiO₂ band gap of about 0.6 eV for optimal nitriding and heat-treated conditions. The TiO₂ NTs annealed at 450 or 650 °C in air (ex situ) and nitrided under UHV conditions were used as reference materials to check the formation of Ti–N bonds in the TiO₂ lattice with a well-defined structure (anatase or a mixture of anatase and rutile). Scanning electron microscopy microscopic observations of the received materials were used to evaluate the morphology of the TiO₂ NTs after each step of the nitriding and annealing treatments.