The redox properties and electronic structures of a series of phenoxo- and hydroxo-bridged dicopper(II) complexes have been explored. Complexes (1a–c)2+ are based on symmetrical ligands with bis(2-methylpyridyl)aminomethyl as complexing arms bearing different substituting R groups (CH3, OCH3, or CF3) in the para position of the phenol moiety. Complex 2a2+ is based on a symmetrical ligand with bis(2-ethylpyridyl)aminomethyl arms and R = CH3, while complex 3a2+ involves an unsymmetrical ligand with two different complexing arms (namely bis(2-ethylpyridyl)aminomethyl and bis(2-methylpyridyl)aminomethyl). Investigations have been done by electrochemical and spectroelectrochemical means and correlated to theoretical calculations as this series of complexes offers a unique opportunity of an in-depth comparative analysis. The voltammetric studies have shown that the redox behavior of the dicopper complexes is not influenced by the nature of the solvent. However, the increase of the spacer chain length and the unsymmetrical design induce significant modifications of the voltammetric responses for both oxidation and reduction processes. DFT calculations of the redox potentials using a computational reference redox couple calculated at the same level of theory to reduce systematic errors confirm these results. Ligand contributions to the electronic structure of the different species have been analyzed in detail. The good agreement between experimental and theoretical results has validated the developed calculation method, which would be used in the following to design new dinuclear copper complexes. These studies demonstrate that subtle modification of the ligand topology can significantly affect the redox and spectroscopic properties. In particular, the unsymmetrical design allows the formation of a transient mixed-valent Cu(II)-Cu(III) phenoxo complex detected upon spectroelectrochemical experiments at room temperature, which evolves toward a dicopper (II,II) phenoxyl complex. The latter displays an intense π → π* transition band at 393 nm in the UV–vis spectrum compared to the less intense ligand to metal charge transfer band at 518 nm observed for the mixed-valent Cu(II)-Cu(III) phenoxo complex.