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Electroreduction of carbon dioxide (CO2RR) has been regarded as a promising approach to realize the production of useful fuels and to decrease greenhouse gas levels simultaneously, where high-efficiency catalysts are required. Herein, we report La2CuO4 nanobamboo (La2CuO4 NBs) perovskite with rich twin boundaries showing a high Faraday efficiency (FE) of 60% toward ethylene (C2H4), whereas bulk La2CuO4 exhibits a FECO of 91%. X-ray absorption spectroscopy (XAS) reveals that the Cu in La2CuO4 NBs is in the Cu2+ state, and no obvious change can be ob