Electrochemical reduction of carbon dioxide (CO2) represents a promising approach to advancing carbon neutrality in a sustainable manner. However, scaling up electrochemical CO2 reduction reaction (CO2RR) for practical applications hinges on the development of efficient catalysts. In this area, transition metal-based catalysts have garnered significant interest due to their tuneable electrochemical properties, which align with the reduction potentials required for converting CO2 into desirable products. Initially, transition metal complexes gained significant attention due to their tuneable electronic structures. However, recent advancements have shown that transition metal nanoparticles exhibit superior catalytic activity, primarily due to their unique intrinsic surface properties. Interestingly, further research has revealed that the structural architecture of these catalysts plays a crucial role in determining their efficacy however controlling such architectures in transition metal-based nanoparticles is challenging. This realization has paved the way for the utilization of transition metal-based nanoclusters (NCs) with precisely defined structural features and optimized surface properties for this purpose. Initially, noble metal-based NCs and their alloys were widely used for this application. However, despite their well-defined architectures and notable surface properties, these NCs predominantly produce CO as the main CO₂RR product, limiting their versatility. In contrast, copper (Cu) NCs stand out due to their unique ability to catalyze CO2RR into a wide array of products, including hydrocarbons and oxygenates due to their ability to stabilize the intermediates. This distinctive behavior makes Cu NCs a key focus in the field.