In summary, the reported work proposes Pd/Ni(OH)₂ catalysts with rich Ni²⁺–O–Pd interfaces for low-potential HMFOR with ~100% FDCA selectivity. At Ni²⁺–O–Pd interfaces, efficient HMFOR originates from the formation of abundant OH* and the decreased activation energy of C–H bonds. It is proved that the construction of metal-metal hydroxide interfaces is very effective for efficient electrocatalytic oxidation of biomass-derived platform molecules. This work provides comprehensive theoretical insights for highly selective synthesis of high-value biomass derived products at low potential through electrocatalytic oxidation technique.