A bromo tricarbonyl rhenium(I) complex with a thiophene-functionalized bis(pyrazolyl) pyridine ligand (L), ReBr(L)(CO) 3 (1), has been synthesized and characterized by variable temperature and COSY 2-D 1 H NMR spectroscopy, single-crystal X-ray diffraction, and photophysical methods. Complex 1 is highly luminescent in both solution and solid-state, consistent with phosphorescence from an emissive 3 MLCT excited state with an additional contribution from a LC 3 (p→ p*) transition. The single-crystal X-ray diffraction structure of the title ligand is also reported.