Starting from anionic tetrazole-based ligands, namely, 5-(4'-cyanophenyl)tetrazolate and 5-(4'-pyridyl)tetrazolate, mononuclear and dinuclear complexes offac-[Re(CO)(3)(phen)](+) (phen = 1,10-phenanthroline) were prepared and characterized. For the mononuclear complexes, regioselective coordination of the metal fragments on the negatively charged tetrazolato ring is exclusively obtained. Coordination to the benzonitrile and pyridine groups was achieved by previous alkylation of the tetrazole ring. Dinuclear complexes were obtained by treatment of the corresponding mononuclear tetrazole-bound complexes with fac-[Re(CO)(3)(phen)(THF)](+). The second rhenium fragment coordinated either to the pyridine ring or, in the case of the benzonitrile ligand, to the tetrazole ring. The electrochemical properties were probed in an imidazolium ionic liquid, highlighting reduction processes centered on the phen ligand and oxidation processes localized on the metal. The photophysical properties of the complexes are characterized by phosphorescent emission from triplet metal-to-ligand charge transfer excited states, with trends in the lifetime and quantum yield in qualitative agreement with the energy gap law. The two dinuclear complexes show almost superimposable emission profiles: in the 5-(4'-cyanophenyl)tetrazolate-bridged complex, the two metal fragments coordinated to the tetrazole are equivalent and share a positive charge of +1. On the other hand, the photophysical properties of the 5-(4'-pyridyl)tetrazolate-bridged dinuclear complex suggest energy transfer between the two metal centers. dinuclear complexes offac-[Re(CO)(3)(phen)](+) (phen = 1,10-phenanthroline)