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Cu(OH)2 nanomaterials are widely investigated for non-enzymatic glucose sensors due to their low-cost and excellent performance. Cu(OH)2 nanomaterials usually grow on substrates to form sensor electrodes. Reported works mainly focus on structure adjusting of the Cu(OH)2 nanostructures, while the optimization of substrates is still lacking. In the present work, directional porous Cu (DPC) was applied as the substrate for the growth of Cu(OH)2 nanograss (NG), and hierarchical structures of Cu(OH)2@DPC were prepared by alkaline oxidation. The morphology and microstructure evolution of the prepared hierarchical structures was investigated, and the non-enzymatic glucose sensing performance was evaluated. Cu(OH)2@DPC exhibits enhanced comprehensive non-enzymatic glucose sensing performance compared to the reported ones, which may benefit from both the effective adsorption of the Cu(OH)2 NG with a relatively high surface area and the high solute exchange of the DPC by a channel effect. This work provides new insights into the further improvement of the non-enzymatic glucose sensing performance of Cu(OH)2 nanostructures by optimizing the substrate structure.