Transition metal complexes featuring redox-activeligands often exhibit multiple redox states, influenced by the interplay between the metal center and the ligand. This study delves into the electronic structures of two mononuclear complexes of copper with two similar redox-active urea azine ligands. The ligands differ by the replacement of an NCH3 moiety by an S atom in the ligand backbone. Experimental analysis yields pronounced electronic structural disparities between these complexes, observable in both the solution and solid phases. Conventional quantum chemical methods, such as density functional theory using different functionals (B3LYP, TPSSh, and CAM-B3LYP), remain inadequate to rationalize the observed spectroscopic anomalies. However, a multiconfigurational approach elucidates the disparate behaviors of these complexes. Multireference perturbation theory, based on complete active space self-consistent field computations identifies Cu(I) in the case of the complex with the NCH3 containing ligands and a state with substantial Cu(II) contributions in the case of the complex with the S atom containing ligands. In contrast, DFT indicates Cu(I) in both scenarios.