The reverse water-gas shift (RWGS) reaction offers a sustainable approach for CO2 utilization, yielding CO for vital catalytic processes. This study compares the catalytic performance of exsolved Cu- and Ni-encapsulated silicalite-1 (S-1) catalysts against those prepared by impregnation methods. Exsolved catalysts, characterized by confined metal nanoparticles and distinct surface chemistry, exhibited higher CO selectivity and lower activation energies of CO formation than their impregnated counterparts. Surface and structural analyses revealed that the exsolution process enhanced RWGS activity, driven by altered metal-support interactions and unique adsorption behaviors, offering insights for improving the efficiency of RWGS catalysis.