The electrooxidation of the alcohol and aldehyde molecules instead of water coupled with H₂ production has been proven to be effective for producing high-value fine chemicals under alkaline conditions. It is also noteworthy that under acidic conditions, the stability of non-noble metal water oxidation catalysts remains a great challenge due to the lattice oxygen mechanism. Hence, we coupled the biomass-derived glucose oxidation for high-value D-glucaric acid (GRA) with ultra-durable hydrogen in acid solution over a Yb-MnO₂ catalyst. The Mn³⁺ regulated by Yb atoms doped in MnO₂ can effectively optimize the adsorption and desorption processes of the alcohol and aldehyde group and improve the intrinsic activity but cannot for H₂O. The catalyst exhibited extremely high activity and stability after 50 h for glucose oxidation, inhibiting the lattice oxygen process and MnO⁴⁻ formation, while the activity was quickly lost within 0.5 h for water oxidation. Density functional theory (DFT) calculations further demonstrated that glucose oxidation reaction proceeds preferentially due to the oxidation of aldehyde group with lower adsorption-free energy (−0.4 eV) than water (ΔG > 0 eV), avoiding the lattice oxygen mechanism. This work suggests that biomass-derived glucose oxidation not only provides a cost-effective approach for high-value chemicals, but also shows an extremely potential as an alternative to acidic oxygen evolution reaction (OER) for ultradurable H₂ production.