Highly resolved emission, excitation, and resonantly line-narrowed spectra, as well as emission decay properties of [Rh(bpy-h(8))(n)(bpy-d(8))(3-n)](3+) (n = 0, 2, 3; bpy = 2,2’-bipyridine) doped into [Zn(bpy-h(8))(3)](ClO4)(2) are presented for the first time. [Rh(bpy-h(8))(3)](3+) and [Rh(bpy-d(8))(3)](3+) exhibit one low-lying triplet T-1 at 12 757 +/- 1 and 22 818 +/- 1 cm(-1), respectively (blue shift 61 cm(-1)), while [Rh(bpy-h(8))(2)(bpy-d(8))](3+) has two low-lying triplets at 22 757 +/- 1 and 22 818 +/- 1 cm(-1). The well-resolved vibrational satellite structures show, that the equilibrium positions of the triplet and the singlet ground S-0 state are not very different and that the force constants in T-1 are mostly slightly smaller than in S-0. Moreover, the vibrational satellite structure is strongly dominated by vibrational ligand modes, which demonstrates the pi pi* character of the corresponding transition. However, the occurrence of several very weak vibrational modes of metal-ligand character displays a small influence of the metal ion.