Advancing Biomass Valorization via Electrocatalytic Oxidation: Design Principles, Emerging Challenges, and Future Perspectives

Electrocatalytic oxidation enables the sustainable conversion of biomass into high‐value chemicals and fuels. However, the field lacks a unified framework linking substrate molecular structures to catalyst design. Herein, biomass substrates are categorized by carbon chain length and structural complexity: C 2 –C 3 alcohols, C 5 –C 7 cyclic compounds, and C n biopolymers. This categorization identifies substrate‐specific reaction bottlenecks, such as the competition between C–C bond cleavage and C–O oxidation, and yields four generalized catalyst design principles, namely, optimizing intermediate adsorption, engineering synergistic multi‐type active sites, accelerating active‐site formation, and maximizing site exposure. Furthermore, the application of operando spectroscopy and machine learning is examined for resolving mechanistic ambiguities and accelerating materials discovery. Finally, this review assesses the macroscopic engineering bottlenecks restricting industrial translation, specifically downstream separation challenges, the limitations of alkaline electrolytes, and the requirements for rigorous techno‐economic and life‐cycle assessments. By bridging molecular‐level design with process engineering, this comprehensive synthesis provides a roadmap for scalable electrocatalytic biorefineries.