LAUSR

Integrating renewable electricity‐powered hydrogen evolution (HER) with oxidative biomass valorization presents a promising strategy to enhance energy utilization and cost‐effectiveness. However, achieving an industrial‐scale production rate at a low potential remains a critical challenge. Herein, a dense dual‐phase NiSe‐CoNiSe2 heterostructure is engineered through sequential hydrothermal and selenization processes. During the electro‐oxidation of 5‐hydroxymethylfurfural (HMFEOR), the spatially separated yet complementary CoNiSe2 and NiSe active components at the interface effectively balance the adsorption kinetics of HMF/intermediates and *OH species, and facilitate sequential C─H/O─H bond cleavage, ultimately unlock a dynamically regulated pathway for reactant capture and processing. This synergistic effect achieves unprecedented HMFEOR performance of Ni/Co‐based catalysts reported to date, including a record‐low onset potential of 1.16 VRHE, a current density of ≈400 mA cm−2 at 1.33 VRHE, and an astonishing 2,5‐furandicarboxylic acid (FDCA) production rate of 430 µmol cm−2 h−1 (at 1.28 VRHE), which breaks the trade‐off between energy consumption and production rate. When applied to coupled HMFEOR‐HER flow electrolysis, the system delivers an industrially viable FDCA output of 4.92 mmol cm−2 h−1 (at 1.50 V). This heterointerface‐driven strategy establishes a scalable platform for energy‐minimized and high‐flux biomass upgrading, advancing the simultaneous production of renewable chemicals and green hydrogen toward industrial feasibility.