Nitrogen-doped TiO2 films were prepared by reactive ion-beam sputtering deposition (IBSD) in a mixed atmosphere of NH3 and O2 at a substrate temperature of 400 °C. X-ray photoelectron spectra revealed the presence of six ions, i.e., N3−, N2−, N1−, N+, N2+, and N3+, respectively, in the films. The amorphous films had complex, randomly oriented chemical bonds. The Tauc–Lorentz model was employed to determine the bandgap energy of the amorphous films prepared using different NH3/O2 gas mixing ratios by ellipsometry. In addition, the optical constants of the films were measured. With the increase in the NH3/O2 gas mixture ratio to 3.0, the bandgap of N-doped TiO2 narrowed to ~2.54 eV.