Investigation of catalytic hydrogenation of CO2 to CO by way of the reverse water-gas shift (RWGS) was undertaken utilizing Ni/SiO2-based catalysts. Among the many array of catalysts examined, the Ni/SiO2 catalyst derived from the discount of Silicalite-1-encapsulated, ligand-protected Ni2+ (Ni0.2@S-1-red) exhibited promising efficiency. This catalyst demonstrated a CO2 conversion charge approaching the equilibrium conversion of RWGS, a selectivity for CO exceeding 99%, and a excessive house time yield of CO (9.7 mol/gNi/h). The outcomes noticed might be attributed to a number of components, specifically the extremely dispersed Ni0 and Niδ+ species, in addition to the presence of bridging oxygen of the Ni-O-Si construction, of which CO2 might be adsorbed reasonably. The reasonably bonded CO2 on Ni0.2@S-1-red permits for the environment friendly desorption of its diminished intermediate, i.e. *CO, ensuing within the technology of gaseous CO at a speedy charge, consequently stopping its deep hydrogenation to CH4. Complementary Density Practical Principle (DFT) calculations had been carried out and revealed that CO molecules have poor adsorption and better adsorption vitality on the Ni@S-1 floor in comparison with the S-1 floor. This helps the speedy desorption of *CO and the noticed excessive selectivity of CO. Furthermore, the structure-activity correlation evaluation additional helps the declare of Ni0.2@S-1-red as a promising RWGS catalyst.