The rapid development of electrochemical CO2 reduction offers a promising route to convert in-termittent renewable energy into products of high value-added fuels or chemical feedstocks. However, low faradaic efficiency, low current density, and a narrow potential range still limited the large-scale application of CO2RR electrocatalyst. Herein, monolith 3D bi-continuous nano-porous Bismuth (np-Bi) electrodes are fabricated via a simple one-step electrochemical dealloying strategy from Pb-Bi binary alloy. The unique bi-continuous porous structure ensures highly effective charge transfer, meanwhile the controllable millimeter-size geometric porous structure enables easy catalyst adjustment to expose highly suitable surface curvatures with abundant reactive sites. This results in a high selectivity of 92.6% and superior potential window (400 mV, selectivity >88%) for electrochemical reduction of carbon dioxide to formate. Our scalable strategy provides a feasible pathway for mass-producing high-performance and versatile CO2 electrocatalysts.