A family of bis(μ-hydroxido)dicopper(II,II) complexes bearing a naphthyridine-based scaffold has been synthesized and characterized. Cyclic voltammetry reveals that the nature of the anions present in the complexes plays a pivotal role in their electrochemical properties. X-ray diffraction, spectroscopic and electrochemical analysis data support the formation of intimate ion pairs by non-covalent interactions driving to a ca. 270 mV difference for the potential required to monooxidize the CuIICuII species.