Leveraging the nm-scale size regime and discrete electronic band structure, atomically precise metal nanoclusters (NCs) have rapidly emerged as a significant area of interest in materials chemistry research. Initially, the focus was predominantly on noble metals, such as gold (Au) and silver (Ag), due to their favorable properties and relative ease of synthesis. However, recent advancements in synthetic methods have expanded the scope of metal NCs to include elements from the first row of the transition metals. The synthesis of these first-row transition metal NCs presents unique challenges, particularly regarding their stability. These clusters often exhibit higher reactivity, making them more prone to degradation or transformation, a characteristic that has historically limited their practical applications. Nonetheless, with improved control over reaction conditions and a deeper understanding of the factors influencing stability, researchers have been able to produce several types of stable first-row transition metal NCs. These advancements have not only demonstrated that stability concerns can be mitigated but also opened up new avenues for exploring the applications of these NCs. Among these, Cu NCs have been emerging very rapidly due to its favorable catalytic properties. The electrochemical reduction of carbon dioxide (CO2) has gained considerable attention for its potential to tackle both environmental and energy issues. Catalysts are essential for increasing the efficiency and selectivity of this reaction, thereby making it more feasible for large-scale implementation. Among the various catalysts studied for this purpose, nanocluster (NC)-based catalysts stand out due to their small size with discrete in nature and distinctive electronic properties. Although copper (Cu) nanoclusters are relatively new compared to their Au and Ag counterparts, they exhibit exceptional binding affinities with CO2 molecules and their intermediates, facilitating the reduction process with a range of the end products. Although the beneficial effects of Cu NCs as catalysts are well-recognized, their limited availability and stability hinder their broader utilization in selective end-product catalytic reactions. To date, only a small number of Cu NCs have been identified and used as electrocatalysts for reduction reactions. Most of these clusters contain only a few Cu atoms, where the geometric architecture influences the selectivity of the resulting end products. For high nuclear Cu NCs, the presence of lattice hydrides significantly influences the mechanistic pathways and product selectivity. However, there is a paucity of literature examining the role of high-nuclear Cu NCs with interstitial hydrides as catalysts. Only one report identified the effect of various high nuclear Cu NCs as catalyst particularly for the conversion of CO2 to CO. Therefore, there is a valuable opportunity to explore how this structural architecture affects the selectivity of different end products. Another significant concern is the oxidation state of the metal atoms within these NCs. The literature indicates that Cu(I) is predominantly present in the structure of Cu NCs used for CO2 reduction reactions (CO2RR). There is a notable scarcity of Cu(0)-containing NCs due to their high reactivity, which makes their stabilization and utilization as catalysts during electrochemical processes particularly challenging. The presence of Cu(0) in the structure of Cu NCs thus presents additional difficulties in employing them as effective catalysts. In the view of the above mentioned facts, here we synthesized [Cu23H4(SC7H7)18(PPh3)6] NC which is constructed by the fusion of two identical geometric solids through fusion of a Cu(0) center. The unique geometric architecture make this NC highly stable although it contain a Cu(0) center and success full loaded on the CB surface without any degradation to serve as a electrochemical catalyst. During the electrochemical process it shows a high selectivity for HCOOH formation although it do not have the lattice hydrides.