Display omitted •Co@NPC was prepared via one-pot pyrolysis using DES as self-template.•Coupling GOR for boosting H2 evolution and production of value-added chemicals.•N-doping optimizes the adsorption energy of H2O and glucose.•Graphitic N could most effectively promote the glucose oxidation reaction. The electrocatalytic water splitting for hydrogen production is greatly limited by the sluggish anodic OER. Herein, a hybrid of cobalt nanoparticles supported in nitrogen doped porous carbon (Co@NPC) is prepared by using a biomass-based ternary deep eutectic solvent (DES) as precursor and self-templates, which is utlized as bifunctional electrocatalyst for boosting H2 generation and converting glucose into valuable chemicals simultaneously. Importantly, only a small cell voltage of 1.56 V is required to deliver 10 mA cm−2, which is 180 mV lower than that of overall water splitting. Density functional theory (DFT) calculations confirm that nitrogen doping porous carbon could synergistically optimize adsorption energies of H2O (ΔE*H2O) and *H adsorption free energies (ΔG*H), enhancing catalytic activity toward HER. This work highlights the potential application prospects of using glucose oxidation reaction (GOR) instead of OER to promote H2 generation and product value-added chemicals.