The increasing emission of carbon dioxide (CO2) into the atmosphere is a major concern in the face of global warming and climate change. Despite efforts, the primary source-fossil fuel combustion to meet energy demands-continues unabated. This situation emphasizes the urgent need for innovative solutions to tackle both environmental degradation and energy sustainability. Amidst this challenge, a promising avenue emerges: harnessing the excess CO2 present in our environment as an energy source. Among the diverse array of CO2-reduction methodologies, the catalyst-induced electrochemical reduction method has garnered significant attention. Once the reduction approach is established, the efficacy of the catalysts has become a paramount global research concern. Consequently, a burgeoning research endeavor is underway worldwide to engineer an optimal catalyst for this electrochemical reduction process. In the course of this journey, transition metal electrocatalysts have demonstrated their superiority over other contenders. However, unravelling the complexities of catalyst performance proves to be a formidable challenge, considering the influential role played by factors such as material structure and size. In response to this challenge, researchers are increasingly directing their attention toward achieving uniformity and smaller sizes, with nanoclusters (NCs) emerging as a promising avenue. Remarkably, gold and silver NCs have demonstrated notable success in efficiently reducing CO2 to CO, a valuable feedstock for the subsequent generation of fuel. However, the focus has shifted to the formation of other NCs for achieving products with even higher energy densities. Among the higher energy density products, methanol (CH3OH) emerges as a standout option, boasting exceptional characteristics such as high energy density, ease of storage, and transportability, making it highly desirable as a fuel source. Furthermore, the versatility of CH3OH extends beyond its role as a fuel. It serves as a raw material across a spectrum of industries including plastics, paints, silicone, and other chemical sectors, underscoring its pivotal importance. Despite its utility, the conventional steam methane reforming and dry reforming method of producing CH3OH emits substantial greenhouse gases under ultra-high pressure and high-temperature conditions, limiting its applicability in sustainable practices. Therefore, there is a growing interest in leveraging the electrochemical reduction of CO2 to selectively produce CH3OH under normal temperature and pressure, offering a near-zero-emission pathway towards achieving carbon neutrality. Recent research has shed light on the remarkable potential of copper (Cu) NCs in electrochemical CO2 reduction. Unlike traditional NC-based catalysts, these Cu NCs possess a unique capability to yield predominant products such as formic acid (HCOOH), carbon monoxide (CO), and hydrocarbons during CO2 reduction. This breakthrough not only expands the repertoire of potential products but also signifies a substantial advancement in the pursuit of efficient CO2 reduction methodologies. While Cu nanoparticles have been utilized in this domain for their versatility in product generation, the utility of Cu NCs remains somewhat limited within certain parameters. Hence, there exists a compelling need to explore the potential of Cu NCs for producing a wider array of valuable products. It has been observed that various factors such as the NC architecture, number of constituent atoms, and ligands play pivotal roles in determining the catalytic activity of Cu NCs. Additionally, defect sites on Cu NCs also play a crucial role in various catalytic reactions, although there is no study yet available on how these defects can tune the specificities of CO2 reduction products. This presents an opportunity to fine-tune the inherent properties of Cu NCs to efficiently produce additional beneficial compounds beyond the regular products.