Among various methods of developing hydrogen energy, electrocatalytic water splitting for hydrogen production is one of the approaches to achieve the goal of zero carbon emissions. It is of great significance to develop highly active and stable catalysts to improve the efficiency of hydrogen production. In recent years, the construction of nanoscale heterostructure electrocatalysts through interface engineering can not only overcome the shortcomings of single-component materials to effectively improve their electrocatalytic efficiency and stability but also adjust the intrinsic activity or design synergistic interfaces to improve catalytic performance. Among them, some researchers proposed to replace the slow oxygen evolution reaction at the anode with the oxidation reaction of renewable resources such as biomass to improve the catalytic efficiency of the overall water splitting. The existing reviews in the field of electrocatalysis mainly focus on the relationship between the interface structure, principle, and principle of catalytic reaction, and some articles summarize the performance and improvement schemes of transition metal electrocatalysts. Among them, few studies are focusing on Fe/Co/Ni-based heterogeneous compounds, and there are fewer summaries on the oxidation reactions of organic compounds at the anode. To this end, this paper comprehensively describes the interface design and synthesis, interface classification, and application in the field of electrocatalysis of Fe/Co/Ni-based electrocatalysts. Based on the development and application of current interface engineering strategies, the experimental results of biomass electrooxidation reaction (BEOR) replacing anode oxygen evolution reaction (OER) are discussed, and it is feasible to improve the overall electrocatalytic reaction efficiency by coupling with hydrogen evolution reaction (HER). In the end, the challenges and prospects for the application of Fe/Co/Ni-based heterogeneous compounds in water splitting are briefly discussed.