The phenoxyl radical binding copper complexes have been widely developed and their detailed geometric and electronic structures have been clarified. While many one-electron oxidized CuII-phenolate complexes have been reported previously, recent studies of the Cu-phenolate complexes proceed toward elucidation of the complexes with other oxidation states, such as the phenoxyl radical binding CuI complexes and CuIV-phenolate complexes in the formal oxidation state. This Perspective focuses on new aspects of the properties and reactivities of various Cu-phenolate and Cu-phenoxyl radical complexes with emphasis on the relationship between geometric and electronic structures.