In this study, we utilized various Pr-doped CeO2 catalysts (Pr=5, 10, 20, and 30 wt.%) as a support medium for the dispersion of cobalt (Co) nanoparticles, aiming to investigate the impact of oxygen vacancies on the water-gas shift (WGS) reaction. Different characterization techniques were employed to understand the insights into the structure-activity relationship governing the performance of Pr doped ceria supported Co catalysts towards WGS reaction. Our findings reveal that Co/Pr-CeO2 catalysts at optimum Pr loading (10 wt.%) exhibit a superior CO conversion (88%) facilitated by the presence of more oxygen vacancies induced by Pr doping into the CeO2 lattice, as opposed to the performance of the pure Co/CeO2 catalytic system. It was also found that the highest activity was obtained at increased intrinsic oxygen vacancies and strong synergy between Co and Pr/CeO2 support, fostering more favorable CO activation at the interfacial sites, thus accounting for the observed enhanced activity.