The development of a bidirectional oxygen reduction reaction (ORR)/ water oxidation reaction (WOR) catalyst is vital for the development of small-molecule activation-based fuel cell technology. Enzyme-inspired synthetic catalyst design has emerged as one of the promising strategies for the construction of such bidirectional catalysts. Here, we have constructed a synthetic copper complex, featuring enzymatic hallmarks such as redox-active ligand and secondary proton relay, that is active for bidirectional ORR/WOR electrocatalysis in aqueous solution. The electrochemical data revealed one of the fastest ORR [2.8(±0.2)×106 s-1] and WOR rates [96000(±8000) s-1] for Cu-based systems in aqueous solutions. This molecular electrocatalyst proceeds via a binuclear homolytic reaction pathway to ensure an exclusive 4e–/4H+ reduction of O2 to H2O, without any partially reduced side products. The bidirectional electrocatalytic ORR/WOR activity for this complex is extended even in organic media (DMF).