Treatment of [Re(CO)5X] (X = Cl, Br) with 2-(2-tert-butyltetrazol-5-yl)pyridine yielded neutral mononuclear complexes by exchange of two CO ligands for the chelating tetrazolato ligand. Treatment of [Re(CO)5Br] with phenyltetrazolate resulted in the assembly of an anionic dinuclear rhenium tricarbonyl species bridged by three tetrazole rings. The reaction of [Re(CO)5Br] with (2-tert-butyltetrazol-5-yl)benzene formed an analogous neutral dinuclear complex bridged by a tetrazole ring as well as two bromide ligands; however this complex was found to be rather unstable in solution and was only structurally characterized via X-ray diffraction. The first three complexes were investigated for their photophysical properties, highlighting phosphorescent emission from their triplet metal-to-ligand charge transfer excited states, although in the case of the dinuclear species the quantum yield was found to be extremely low. The complexes are also characterized for their electrochemical behavior, and while the neutral mononuclear species show irreversible oxidations, the dinuclear complex displays one reversible and simultaneous two-electron oxidation.