Non-stoichiometric NbxNy coatings, produced in a reactive sputtering process, were analyzed on the basis of their chemical composition (specifically, nitrogen concentration) and its relationship with electrical conductivity. The chemical composition and bonding configuration were examined using X-ray photoelectron spectroscopy (XPS), revealing Nb–N bonds. The stoichiometry variation dependence on the N2 flow was also analyzed, using Auger electron spectroscopy (AES). Without exposing the samples to air, a normal behavior was observed; meaning that the nitrogen concentration in the coatings increased, with an increase in N2 flow. The electrical properties were evaluated and their relationship with nitrogen content in the films was analyzed. The highest conductivity value for all studied samples was observed for the sub-stoichiometric film, NbN0.32, which also exhibited a positive Hall coefficient. It indicated that the conduction was mainly dominated by hole-type carriers. High conductivity at lower nitrogen content was attributed to the fact that, at a low concentration of nitrogen, the effect of impurities, acting as dispersion points for electrons, was lower, increasing the relaxation time. As the main conclusion, the Ar/N2 flow ratio strongly influenced the coatings of stoichiometry and then, this stoichiometry affected, to a great extent, the electrical conduction and the Hall coefficient of the coatings.