A dinuclear Cu(I) molecular electrocatalyst was developed for the conversion of CO₂ into C₃ products. The catalyst, a Br-bridged dinuclear Cu(I) complex, efficiently produces C₃H₇OH with high robustness during the reaction. Experimental operando surface-enhanced Raman scattering analysis and theoretical quantum-chemical calculations revealed the formation of a C–C coupling intermediate species between the two Cu centres. The molecular design of the catalyst enables the generation of multicarbon CO₂ reduction products. The electrochemical CO₂ reduction reaction (CO₂RR) is a promising technology for producing valuable chemical feedstocks and fuels, and is crucial for sustainable carbon-neutral economies. CO₂RR can significantly reduce the use of fossil fuels and help control the anthropogenic carbon cycle. The reaction requires efficient electron and proton transfer to CO₂, and multicarbon products like ethylene and ethanol, which require C–C coupling, are highly valuable. However, the synthesis of C₃ products, such as C₃H₇OH, remains challenging. Molecular catalysts offer potential solutions by enabling precise control over CO₂ reduction. The dinuclear Cu(I) complex with a Br-bridging ligand was synthesized and characterized, showing enhanced CO₂ adsorption and retention. Operando X-ray absorption fine structure (XAFS) analysis confirmed the stability of the catalyst during CO₂ electrolysis. The catalyst was tested in an H-type cell, achieving high Faradaic efficiencies for C₃H₇OH production. Operando spectroscopic analysis identified important intermediates from C–C coupling, and DFT calculations supported the proposed mechanism. The catalyst's structure and stability were maintained during the reaction, and the Cu(I) state was preserved. The results demonstrate the effectiveness of the dinuclear Cu(I) complex in producing C₃H₇OH through C–C coupling, offering a promising approach for the selective synthesis of multicarbon CO₂ reduction products.A dinuclear Cu(I) molecular electrocatalyst was developed for the conversion of CO₂ into C₃ products. The catalyst, a Br-bridged dinuclear Cu(I) complex, efficiently produces C₃H₇OH with high robustness during the reaction. Experimental operando surface-enhanced Raman scattering analysis and theoretical quantum-chemical calculations revealed the formation of a C–C coupling intermediate species between the two Cu centres. The molecular design of the catalyst enables the generation of multicarbon CO₂ reduction products. The electrochemical CO₂ reduction reaction (CO₂RR) is a promising technology for producing valuable chemical feedstocks and fuels, and is crucial for sustainable carbon-neutral economies. CO₂RR can significantly reduce the use of fossil fuels and help control the anthropogenic carbon cycle. The reaction requires efficient electron and proton transfer to CO₂, and multicarbon products like ethylene and ethanol, which require C–C coupling, are highly valuable. However, the synthesis of C₃ products, such as C₃H₇OH, remains challenging. Molecular catalysts offer potential solutions by enabling precise control over CO₂ reduction. The dinuclear Cu(I) complex with a Br-bridging ligand was synthesized and characterized, showing enhanced CO₂ adsorption and retention. Operando X-ray absorption fine structure (XAFS) analysis confirmed the stability of the catalyst during CO₂ electrolysis. The catalyst was tested in an H-type cell, achieving high Faradaic efficiencies for C₃H₇OH production. Operando spectroscopic analysis identified important intermediates from C–C coupling, and DFT calculations supported the proposed mechanism. The catalyst's structure and stability were maintained during the reaction, and the Cu(I) state was preserved. The results demonstrate the effectiveness of the dinuclear Cu(I) complex in producing C₃H₇OH through C–C coupling, offering a promising approach for the selective synthesis of multicarbon CO₂ reduction products.