A series of organometallic copper complexes in formal oxidation states ranging from +1 to +3 have been characterized by a combination of Cu K-edge X-ray absorption (XAS) and Cu Kβ valence-to-core X-ray emission spectroscopies (VtC XES). Each formal oxidation state exhibits distinctly different XAS and VtC XES transition energies due to the differences in the Cu Z_eff, concomitant with changes in physical oxidation state from +1 to +2 to +3. Herein, we demonstrate the sensitivity of XAS and VtC XES to the physical oxidation states of a series of N-heterocyclic carbene (NHC) ligated organocopper complexes. We then extend these methods to the study of the [Cu(CF₃)₄]⁻ ion. Complemented by computational methods, the observed spectral transitions are correlated with the electronic structure of the complexes and the Cu Z_eff. These calculations demonstrate that a contraction of the Cu 1s orbitals to deeper binding energy upon oxidation of the Cu center manifests spectroscopically as a stepped increase in the energy of both XAS and Kβ_2,5 emission features with increasing formal oxidation state within the [Cun+(NHC₂)]ⁿ⁺ series. The newly synthesized Cu(III) cation [Cu^III(NHC₄)]³⁺ exhibits spectroscopic features and an electronic structure remarkably similar to [Cu(CF₃)₄]⁻, supporting a physical oxidation state assignment of low-spin d⁸ Cu(III) for [Cu(CF₃)₄]⁻. Combining XAS and VtC XES further demonstrates the necessity of combining multiple spectroscopies when investigating the electronic structures of highly covalent copper complexes, providing a template for future investigations into both synthetic and biological metal centers.