The atomic-level tunability of molecular structures is a compelling reason to develop homogeneous catalysts for challenging reactions such as the electrochemical reduction of carbon dioxide to valuable C-1-C-n products. Of particular interest is methane, the largest component of natural gas. Herein, we report a series of three isomeric rhenium tricarbonyl complexes coordinated by the asymmetric diimine ligands 2-(isoquinolin-1-yl)-4,5-dihydrooxazole (quin-1-oxa), 2-(quinolin-2-yl)-4,5-dihydrooxazole (quin-2-oxa), and 2-(isoquinolin-3-yl)-4,5-dihydrooxazole (quin-3-oxa) that catalyze the reduction of CO2 to carbon monoxide and methane, albeit the latter with a low efficiency. To our knowledge, these complexes are the first examples of rhenium(I) catalysts capable of converting carbon dioxide into methane. Re(quin-1-oxa)(CO)(3)Cl (1), Re(quin-2-oxa)(CO)(3)Cl (2), and Re(quin-3-oxa)(CO)(3)Cl (3) were characterized and studied using a variety of electrochemical and spectroscopic techniques. In bulk electrolysis experiments, the three complexes reduce CO2 to CO and CH4. When the controlled-potential electrolysis experiments are performed at -2.5 V (vs Fc(+/0)) and in the presence of the Bronsted acid 2,2,2-trifluoroethanol, methane is produced with turnover numbers that range from 1.3 to 1.8. Isotope labeling experiments using (CO2)-C-13 atmosphere produce (CH4)-C-13 (m/z = 17) confirming that methane originates from CO2 reduction. Theoretical calculations are performed to investigate the mechanistic aspects of the 8e(-)/8H(+) reduction of CO2 to CH4. A ligand-assisted pathway is proposed to be an efficient pathway in the formation of CH4. Delocalization of the electron density on the (iso)quinoline moiety upon reduction stabilizes the key carbonyl intermediate leading to additional reactivity of this ligand. These results should aid the development of more robust catalytic systems that produce CH4 from CO2.