The development of molecular catalysts and materials that can convert carbon dioxide (CO2) into a value-added product is a great chemical challenge. Molecular catalysts set benchmarks in catalyst investigation and design, but their incorporation into solid-state materials, and optimization of the electrochemical operating conditions, is still needed. For example, rhenium(I) diimine catalysts show almost quantitative selectivity for the conversion of CO2 to carbon monoxide (CO) in acetonitrile (MeCN), but the modification of diimine backbones can be challenging if the goal is to incorporate such molecules into materials. Presented here is a rhenium(I) complex with a 2-(2'-quinolyl)benzimidazole (QuBIm-H) ligand, where N-alkylation with a pyrene derivative allows access to a catalyst that can be adsorbed onto electrodes for aqueous CO2 reduction chemistry. The rhenium(I) catalysts are inactive for homogeneous CO2 reduction in MeCN. However, when adsorbed on edge-plane graphite, the same complexes show good activity for heterogeneous aqueous CO2 reduction, with 90% selectivity for CO. Comparative electrochemical studies between covalent and noncovalent modification of the graphite surfaces were also carried out for related rhenium(I) tricarbonyl complexes.