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The exploration of novel systems for the electrochemical CO2 reduction reaction (CO2 RR) for the production of hydrocarbons like CH4 remains a giant challenge. Well-designed electrocatalysts with advantages like proton generation/transferring and intermediate-fixating for efficient CO2 RR are much preferred yet largely unexplored. In this work, a kind of Cu-porphyrin-based large-scale (≈1.5 μm) and ultrathin nanosheet (≈5 nm) has been successfully applied in electrochemical CO2 RR. It exhibits a superior FE CH 4 of 70 % with a high curre