Designing efficient photo/electro-catalysts for hydrogen production from water splitting is considered as one of the most promising technologies for renewable energy utilization. It is reasonable to substitute the anodic oxygen evalution reaction with some more favorable oxidizable reactions, such as the oxidation of benzyl alcohol, which can not only provide an environmentally friendly synthesis of value-added benzaldehyde and benzoic acid, but also significantly reduce the overpotential of hydrogen production from water splitting. Such hydrogen production coupled with environmentally friendly organic synthesis technology has attracted great attention in recent years. Herein, the research progress of photo/electro-catalytic hydrogen production from water splitting coupled with the green oxidation of benzyl alcohol is systemically summarized in recent years, especially in the mechanism of catalytic oxidation of benzyl alcohol by constructing catalysts with different surface morphologies, defect engineering and doping. The preparation strategies of high-efficient photo/electro-catalysts, photo/electro-chemical properties and the mechanism are also summarized in detail. In the field of photocatalysis, the methods of inhibiting the recombination of photogenerated electrons and holes and activating the active sites of the surface/interface of catalysts have been introduced. In the field of electrocatalysis, some effective strategies were also described, such as screening the effective active sites of catalysts, improving the electrical conductivity and the intrinsic activity of catalysts and the integrated technology of electrocatalysis and membrane separation. In addition, bifunctional catalysts are designed for the hydrogen production from water splitting and the selective oxidization of benzyl alcohol with high efficiency and low energy consumption. Finally, the research challenges and opportunities were proposed to shed light on further development of the photo/electro-catalysts for the coupling of water decomposition to hydrogen production and environmentally friendly synthesis of high value-added products from different perspectives and aspects.