Spectrally resolved scanning tunneling microscope-induced luminescence has been obtained under ambient conditions, i.e., at room temperature, in air, by passivating the sample surface with sulfur. This passivation turned out to be essential to suppress the local anodic oxidation induced by the tunneling current. From the dependence of the luminescence signal on tunneling current and voltage, we find that the passivation solution and post-passivation annealing temperature strongly modify the surface density of states (SDOS). More specifically, we found evidence that, after annealing at 400 °C, no SDOS is left above the bottom of the conduction band. For annealing at 200 °C, the SDOS is found to be extended up to 1.0±0.2 eV above the bottom of the conduction band. In all cases, the passivated (001) surface appears to be completely pinned.