<p>Atomic-level catalysts hold immense promise for advancing the atomic economy and facilitating targeted design in catalysis and energy applications. Nevertheless, conventional synthetic approaches have fallen short in attaining the utmost synergy among activity, selectivity, and stability. In this innovative study, a groundbreaking photo-induced neighbour-deposition strategy is introduced to construct diatomic Pt sites on highly dispersed CeO₂ nests for the reverse water-gas shift (RWGS) reaction. In stark contrast to traditional electrostatic adsorption and impregnation techniques, our strategy enables the precise and directional deposition of diatomic sites onto designated regions, effectively circumventing the adverse effects of residual chlorine on catalytic performance. The resultant dual-atom Pt catalyst showcases remarkable RWGS capabilities across a broad temperature spectrum, with CO₂ conversion approaching thermodynamic equilibrium and near-100% CO selectivity. The enhanced catalytic performance is primarily attributed to electron coupling at diatomic Pt sites, which significantly accelerates H₂ dissociation and thence promotes the formation of oxygen vacancies on CeO₂ nests, ultimately improving the hydrogenation process. Furthermore, it exhibits exceptional stability over a 100-h reaction period owing to the strong confinement effect at CeO₂ nests. This research provides a universal strategy for precisely controlling the configuration and coordination structure of active sites in the synthesis of various low-nuclearity cluster catalysts.</p>