The synthesis, structural, and photophysical properties of a novel family of neutral fac-[Re(N∧N)(CO)3(L)] complexes, where N∧N is either 2,2′-bipyridine or 1,10-phenanthroline and L is a para functionalized 5-aryltetrazolate [namely, 5-phenyltetrazolate (Tph-), 4-(tetrazolate-5-yl)benzaldehyde (Tbdz-), 5-(4-acetylphenyl)tetrazolate (Tacy-), and methyl 4-(tetrazolate-5-yl)benzoate (Tmeb-)] are reported. The complexes were prepared by direct addition of the corresponding tetrazolate anion to the acetonitrile solvated fac-[Re(N∧N)(CO)3]+ precursor. NMR data demonstrate that the coordination of the metal fragment is regiospecific at the N2 atom of the tetrazolate ring. These conclusions are also supported by X-ray structural determinations. Photophysical data were obtained in diluted and deaerated dichloromethane solutions displaying broad and structureless profiles with emission maxima ranging from 566 to 578 nm. The absorption profiles indicate the presence of higher energy intraligand (IL) π-π* transitions and lower energies ligand-to-ligand charge transfer (LLCT) and metal-to-ligand charge transfer (MLCT). As the last two transitions are mixed, they are better described as a metal-ligand-to-ligand charge transfer (MLLCT), a result that is also supported by density functional theory (DFT) calculations. The complexes show excited state lifetime values ranging from 102 to 955 ns, with associated quantum yield between 0.012 and 0.099. Compared to the parent neutral chloro or bromo [Re(N∧N)(CO)3X], the complexes show a slightly improved performance because of the π accepting nature of the tetrazolato ligand. The metal-to-ligand backbonding is in fact depleting the Re center of electron density, thus widening the HOMO-LUMO gap and reducing the non-radiative decay mechanism in accordance with the energy gap law. Finally, the electron-withdrawing or donating nature of the substituent on the phenyltetrazolato ligand allows the fine-tuning of the photophysical properties.