Under gas phase conditions, the [Cu(PhO)(PhOH)](+) complex is composed of copper(I), a phenoxy radical bound via the oxygen atom, and a phenol bound via the aromatic ring. Effects of additional ligand coordination on the molecular and electronic structure of the complex [Cu(PhO)(PhOH)](+) are investigated by mass spectrometric and quantum chemical means for [Cu(PhO)L](+) (L = H2O, CH3OH, tetrahydrofuran, NH3, pyridine, imidazole, 1,2-dimethoxyethylene, N,N,N',N'-tetramethylethylenediamine, pyrrole, and thiophene) and [Cu(PhO)(PhOH)Ln](+) (L = H2O, NH3, and 4-methylimidazole) models. The nature and number of additional ligands critically influences the spin distribution in the complex, which is sensitively reflected by the phenoxy CO stretching mode.