Resonance Raman (RR) spectroscopy has been employed to study coordinated phenoxyl radicals (M = Ga, Sc, Fe) which were electrochemically generated in solution by using 1,4,7-triazacyclononane-based ligands containing one, two, or three p-methoxy or p-tert-butyl N-substituted phenolates, i.e., 1,4,7-tris(3,5-di-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclononane (L-3(but)), 1,4,7-tris(3-tert-butyl-5-methoxy-2-hydroxybenzyl)-1,4,7-triazacyclononane (L-3(met)), 1,4-bis(3-tert-butyl-5-methoxy-2-hydroxybenzyl)-7-ethyl-1,4,7-triazacyclononane L-2(met), and 1-(3-tert-butyl-5-methoxy-2-hydroxybenzyl)-4,7-dimethyl-1,4,7-triazacyclononane (L-1(met)). A selective enhancement of the vibrational modes of the phenoxyl chromophores is achieved upon excitation in resonance with the pi --> pi* transition at ca. 410 nm. The interpretation of the spectra was supported by quantum chemical (density functional theory) calculations which facilitate the vibrational assignment for the coordinated phenoxyl radicals and provide the framework for correlations between the RR spectra and the structural and electronic properties of the radicals. For the uncoordinated phenoxyl radicals the geometry optimization yields a semiquinone character which increases from the unsubstituted to the p-methyl- and the p-methoxy-substituted radical. This tendency is indicated by a steady upshift of the nu(8a) mode which predominantly contains the C-ortho-C-meta stretching coordinate, thereby reflecting strengthening of this bond. The calculated normal-mode frequencies for these radicals are in a good agreement with the experimental data constituting a sound foundation for extending thr vibrational analysis to the 2,6-di-tert-butyl-4-methoxyphenoxyl which is the building block of the macrocyclic ligands L-3(met), L-2(met), and L-1(met).