The electrochemical reduction of carbon dioxide (CO₂RR) utilizing intermittent electricity from renewable energy sources represents an emerging and promising approach to achieve carbon neutrality and mitigate the greenhouse effect. This review comprehensively summarizes recent advances in Cu-based metal–organic framework (MOF) electrocatalysts for CO₂RR, focusing on their applications in producing C₁ and C₂₊ products. This paper highlights key strategies such as nanostructure manipulation, multi-component tandem catalysis, single-atom alloying, and ligand functionalization to optimize the binding energies of intermediate species and promote selective CO₂RR pathways. Numerous examples are presented, showcasing remarkable Faradaic efficiencies and product selectivities achieved through rational catalyst design. Furthermore, the use of MOF-derived materials and composites with other materials, like carbon nanotubes, graphene, and metal oxides, is discussed to enhance conductivity, stability, and selectivity. Despite the significant progress, challenges remain in achieving stable and scalable catalysts with high activity and selectivity towards specific C₂₊ products. This review underscores the importance of precise control of catalyst composition, structure, and surface properties to tackle these challenges and provides valuable insights for future research directions in developing advanced Cu-based MOF electrocatalysts for practical applications in CO₂ conversion technologies.

Electrochemical CO₂ reduction reaction (CO₂RR) is a key technology for achieving carbon neutrality and efficient utilization of renewable energy, capable of converting CO₂ into high-value-added carbon-based fuels and chemicals. Copper (Cu)-based catalysts have attracted significant attention due to their unique performance in generating multi-carbon (C₂₊) products such as ethylene and ethanol; however, there are still many controversies regarding their complex reaction mechanisms, active sites, and the dynamic evolution of intermediates. In situ Raman spectroscopy, with its high surface sensitivity, applicability in aqueous environments, and precise detection of molecular vibration modes, has become a powerful tool for studying the structural evolution of Cu catalysts and key reaction intermediates during CO₂RR. This article reviews the principles of electrochemical in situ Raman spectroscopy and its latest developments in the study of CO₂RR on Cu-based catalysts, focusing on its applications in monitoring the dynamic structural changes of the catalyst surface (such as Cu⁺, Cu⁰, and Cu²⁺ oxide species) and identifying key reaction intermediates (such as *CO, *OCCO(*O=C-C=O), *COOH, etc.). Numerous studies have shown that Cu-based oxide precursors undergo rapid reduction and surface reconstruction under CO₂RR conditions, resulting in metallic Cu nanoclusters with unique crystal facets and particle size distributions. These oxide-derived active sites are considered crucial for achieving high selectivity toward C₂₊ products. Time-resolved Raman spectroscopy and surface-enhanced Raman scattering (SERS) techniques have further revealed the dynamic characteristics of local pH changes at the electrode/electrolyte interface and the adsorption behavior of intermediates, providing molecular-level insights into the mechanisms of selectivity control in CO₂RR. However, technical challenges such as weak signal intensity, laser-induced damage, and background fluorescence interference, and opportunities such as coupling high-precision confocal Raman technology with in situ X-ray absorption spectroscopy or synchrotron radiation Fourier transform infrared spectroscopy in researching the mechanisms of CO₂RR are also put forward.