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A group of silica-ionic liquid supported Ru-based catalysts was synthesized and further utilized for CO2 hydrogenation reaction. All the materials were properly analyzed in terms of their physicochemical properties. The physiochemical impacts of different functionalized and non-functionalized ionic liquid over the synthesis, size, and stability of Ru NPs along with their effect on the rate of hydrogenation reaction were investigated. The Ru-[DAMI][NTf2] (1:10)@SiO2 furnished the best catalytic performance in CO2 conversion to formic acid under high-pressure reaction condition. The results confirmed the impact of ionic liquids as a repellent to avoid agglomeration and oxidation of the Ru nanoparticles followed by space resistance and electrostatic protection. Hence, such influence positively begins the rate of reaction as well as the selectivity of the process. Good physiochemical stability of catalyst in terms of 7-time catalyst recycling and easy product/catalyst isolation make this protocol near to the principal of sustainable chemistry.