The valence-to-core (V2C) portion of x-ray emission spectroscopy (XES) measures the electron states close to the Fermi level. These states are involved in bonding, thus providing a measure of the chemistry of the material. In this article, we show the V2C XES spectra for several niobium compounds. The Kβ″ peak in the V2C XES results from the transition of a ligand 2s electron into the 1s core-hole of the niobium, a transition allowed by hybridization with the niobium 4p. This location in energy of this weak peak shows a strong ligand dependence, thus providing a sensitive probe of the ligand environment about the niobium.