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The electrochemical process of coupling electrocatalytic CO2 reduction and organic conversion reaction can effectively reduce the reaction overpotential and obtain value‐added chemicals. Moreover, because of the diversity of substrates and the designability of coupling forms, more and more attention has been paid to this field. This review systematically summarizes the research progress of coupling electrolysis in recent years, (1) co‐electrolysis of CO2 and organics at the cathode to obtain specific products with high selectivity, (2) replacing traditional anodic oxygen evolution reaction (OER) with other valuable oxidation reactions to improve energy utilization efficiency and economic benefits of CO2 conversion, (3) in an electrolytic cell without membrane, the cathode and anode jointly transform CO2 and organics to redox products. We hope that the examples and insights on coupling electrolysis introduced in this review can inspire researchers to further explore and innovate in this direction.

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