A series of novel Re(I)-based heterobimetallic complexes were synthesized using the ligand p-[N-2-(2′-pyridyl)benzimidazolyl]-[N-2-(2′-pyridyl)indolyl]-benzene (L1), which contains two distinct N^N- and N^C-chelating sites. Their photophysical and electrochemical properties were fully characterized, which unveil the existence of electronic communication between the two metal centers. An electrochemical study shows that these types of Re(I) complex are promising candidates as catalysts for electrocatalytic CO₂ reduction.