Efficient coupling of economically favorable electro-oxidation reactions with the hydrogen evolution reaction (HER) has been considered as a promising way to realize synergistic production of hydrogen and value-added chemicals. In this work, a supported nickel molybdenum oxide catalyst was fabricated, which exhibits enhanced activity towards the benzyl alcohol oxidation reaction (BOR) benefited from the enriched active sites. Further investigations indicate that the nearly complete conversion from benzyl alcohol (BA) to the benzoic acid (BC) product can be achieved with simultaneously realized high selectivity and high faradaic efficiency (FE) for long-term operation. The efficient catalyst explored in this work could offer a new material platform for coupled production and value-added benzoic acid and hydrogen.