CO2, a predominant anthropogenic greenhouse gas, emerges as a primary factor in climate change due to the increasing utilization of fossil fuels, necessitating immediate efforts for the development and implementation of strategies like carbon capture and storage (CCS) to mitigate emissions, considering the ongoing dependence on unsustainable energy and transportation resources. The research endeavours to meet the critical requirement for effective CO2 capture through the exploration of novel sorbent materials, with a specific focus on molecularly precise nanoclusters (NCs), aiming to enhance understanding of the catalytic mechanisms in CO2 reduction and design stable, high‐performance sorbents with controllable properties. Advancing the field, the study delves into the synthesis and examination of molecularly precise nanoclusters (NCs), an emerging domain in nanoscience, with a particular emphasis on well‐defined nanoclusters like thiolate‐protected Au, Ag, and Cu NCs. This strategy provides a distinctive foundation for attaining atomic‐level understanding of electrocatalytic CO2 reduction mechanisms, offering a more precise and customized synthesis to overcome challenges associated with polydispersity in conventional nanoparticles. The study highlights the exceptional catalytic activity of specific Au NCs like Au25 in converting CO2 to CO. It surpasses thermodynamic limits. The study also investigates the influence of surface properties, electrostatic, and steric stability on preventing nanocluster aggregation. It emphasizes the potential of molecularly precise nanoclusters as catalysts for CO2 reduction. Additionally, it suggests avenues for advanced sorbent development with improved performance and stability.