The diversity of the structures and new topology discovered in metal-organic compounds are attributed to the selection of metal centers and organic compounds. Numerous recent reports demonstrated that copper ions form complexes with organic ligands with versatility, in which copper atoms have +1, +2, mixed-valence state, and/or Cu-Cu bonds. Although mixed-valence copper coordination compounds may be generated from either oxidation or reduction reactions of copper ions, most known examples were obtained from the reduction route. The oxidation reaction routes for the synthesis of new mixed-valence compounds with metal-metal bonds will be presented.