The development of electrocatalysts that convert CO2 and N2 in flue gas to directly usable urea does not only explore the hidden value of exhaust gas but also alleviates the global environmental issues caused by excessive CO2 emissions; yet, related research studies are still in their infancy. Herein, multi-porous Cu–W18O49@ZIF-8, composed of ultra-small nanosized ZIF-8 on Cu-doped W18O49 nanowires, was fabricated as a urea-generation electrocatalyst in flue gas. It exhibits an appealing Faraday efficiency of urea up to 16.1% at −0.9 V (vs. RHE) and an outstanding yield of 1.33 mmol g−1 h−1 at −1.0 V (vs. RHE) under the flue gas atmosphere. The catalytic performance was maintained for a wide range of N2 : CO2 ratios. Theoretical calculations indicate that the doped copper regulates the electron density around the adjacent W–W, which facilitates N2 adsorption, partly suppresses the HER side reaction, and decreases the ΔG of the following multi-step hydrogenation after *CO insertion until urea production.
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