<p>Hydrogen production coupled with small molecule oxidation derived by renewable energy power has been widely studied as an effective method to reduce energy consumption and prepare added value production. Here, the copper-cobalt phosphide with a multilevel structure has been designed based on the hard and soft acids and bases theory. The nanocone composed of lamellas presented a sharp tip, which a positive effect on the mass transfer enhanced by a local electric field, and the nanolamellas contain CoP/Cu₃P interface provide the highly selective active site for the gluconic acid (GNA) synthesis and hydrogen evolution. The catalyst can drive hydrogen evolution at 5 A·cm⁻² up to 437&#xa0;h without active decay, and the electrocatalytic glucose oxidation at anode presents high efficiency due to Cu (I) introduction and the synergetic effect between interfaces. Density functional theory (DFT) calculation shows that water splitting more readily occurs at the CoP, which provides adsorbed H and −OH for hydrogen evolution and glucose oxidation, respectively, and glucose adsorption more readily occurs at the Cu₃P, which presents lower conversion energy for high value-added GNA. Efficient hydrogen evolution and glucose conversion indicate its high intrinsic activity and synergetic effect. This work provides a special interface construction strategy for the catalytic conversion of hydrogen and small molecules.</p> Graphical abstract <p></p>