Abstract: Production of high value-added chemicals and fuels from carbon dioxide (CO2) is an im⁃portant technology to achieve zero carbon emissions. However, how to efficiently and sustainablyconvert carbon dioxide into higher value long-chain molecules is still a challenge. Compared with tradi⁃tional thermochemical techniques, electrocatalytic reduction can achieve high product selectivity undermilder conditions, and can also be coupled with bioconversion techniques to convert short carbon chainmolecules into long carbon chain products with higher added value. This paper reviews the state of theart of key factors affecting electrocatalytic CO2 reduction performance, including electrodes, catalysts,ion exchange membranes and electrolytes. By adjusting the electronic structure, surface structure andcoordination environment of the copper-based catalysts, the carbon-carbon coupling reaction can beeffectively strengthened, and the Faraday efficiency of C2+ products can be significantly improved atampere-level current density. Furthermore, the research progress on the coupling of CO2 electroreduc⁃tion with microbial conversion to extend the carbon chain is reviewed, which mainly illustrates the ad⁃vantages and challenges of this coupling technology from the perspectives of in situ and ex situ couplingmodes.