Electrocatalytic hydrogenation is an efficient and environmentally friendly way to convert biomass derivatives into high-value-added chemicals and biofuels, although in most cases, the Faraday efficiency (FE) is low. Herein, Cu electrocatalysts with a bicontinuous nanoporous structure and high specific surface area were fabricated by chemical dealloying of CuAl alloy. For the electrocatalytic hydrogenation of furfural to furfuryl alcohol, as a biomass-derived platform molecule reaction, the nanoporous Cu (NP-Cu) exhibited excellent selectivity and high Faraday efficiency by fluidized electrocatalysis. Compared with a commercial Cu sheet electrode, the selectivity of furfuryl alcohol increased from 22 to 96%, and FE increased from 17 to 95%, respectively. The selectivity and FE of Cu nanoparticles for furfuryl alcohol were only about 44% under the same conditions as NP-Cu. It was indicated that the NP-Cu with a high specific surface area provided enough hydrogen adsorption sites (H ads ), leading to the enhancement of electrocatalytic hydrogenation and reduction of electrocondensation in the fluidization. Meanwhile, the hydrogen evolution as a side reaction was also restrained under a relatively low potential. These provide important basis and reference for the development of nanoporous catalysts and electrocatalytic conversion of biomass.