Catalytic transformation of CO2 into CO via the reverse water gas shift (RWGS) reaction is a potential route for establishing a closed carbon loop. However, considering the competitive Sabatier reaction, the catalytic performance is at the heart of the process. In this context, we have developed a novel nanocatalyst (NC) composed of oxygen vacancy (OV) enriched atomic CoOx cluster (CoOOV) decorated Pd nanoparticles (NPs) on the cobalt-oxide support underneath (denoted as CoPd-CoOOV). The as-prepared CoPd-CoOOV NC initiated the RWGS reaction at a temperature of 423 K in the reaction gas (CO2 : H2 = 1 : 3) while delivering an optimum CO production yield of ∼4052 μmol per g catalyst with a CO selectivity of ∼94% at a temperature of 573 K. The cross-referencing results of physical investigations combined with electrochemical analysis suggest that such a high activity and selectivity of the CoPd-CoOOV NC originates from the synergistic cooperation between the neighbouring active sites on its surface, where the high density of OV and adjacent Pd domains synergistically trigger CO2 activation and H2 dissociation, respectively. Besides, the cobalt oxide support underneath served as an electron donor to Pd domains for facilitating H2 splitting. We envision that the obtained results will motivate for designing highly active and selective catalysts for the RWGS reaction.