We present herein a Cp*Co(III)-half-sandwich catalyst system for electrocatalytic CO 2 reduction in aqueous acetonitrile solution. In addition to an electron-donating Cp* ligand (Cp* = pentamethylcyclopentadienyl), the catalyst featured a proton-responsive pyridyl-benzimidazole-based N,N-bidentate ligand. Owing to the presence of a relatively electron-rich Co center, the reduced Co(I)-state was made prone to activate the electrophilic carbon center of CO 2 . At the same time, the proton-responsive benzimidazole scaffold was susceptible to facilitate proton-transfer during the subsequent reduction of CO 2 . The above factors rendered the present catalyst active toward producing CO as the major product over the other potential 2e/2H + reduced product HCOOH, in contrast to the only known similar half-sandwich CpCo(III)-based CO 2 -reduction catalysts which produced HCOOH selectively. The system exhibited Faradaic efficiency (FE) of ~70% while the overpotential for CO production was found to be 0.78 V as determined by controlled-potential electrolysis experiment.