<p>Utilizing solar photothermal catalysis to convert CO₂ into high-value chemicals represents a promising and sustainable strategy for efficient carbon recycling. However, precise regulation of catalytic active sites and light-harvesting materials to improve photothermal-catalytic performance remains a significant challenge. Herein, we report the rational integration of three-dimensional ordered macroporous (3DOM) CeO₂ with positively-charged (Ni^<i>δ</i>+)_<i>n</i> clusters to construct efficient photothermal catalysts for reverse water gas shift (RWGS) reactions. The 3DOM architecture exhibits distinct advantages in enhancing light absorption, improving access to active sites, and providing a unique confined environment for reactant enrichment. Engineering (Ni^<i>δ</i>+)_<i>n</i> clusters within 3DOM CeO₂ not only affords highly active sites for H₂ adsorption and dissociation, but also modulates the local structure of CeO₂ to promote CO₂ adsorption and activation. Furthermore, the (Ni^<i>δ</i>+)_<i>n</i> clusters significantly enhances light-harvesting capability of the catalyst across the UV-vis-NIR spectrum, generating a pronounced photothermal effect that accelerates the reaction kinetics. As a result, the optimized (Ni^<i>δ</i>+)_<i>n</i>/CeO₂ catalyst exhibits outstanding photothermal catalytic performance, achieving a remarkable CO production rate of 63.36 mmol g⁻¹ h⁻¹ in a flowing reaction, with CO selectivity of 93%, under simulated solar irradiation (2.6 W cm⁻²). Theoretical calculations reveal that the (Ni^<i>δ</i>+)_<i>n</i>/CeO₂ catalyst reduces the thermodynamic energy barrier for *COOH formation in CO₂ hydrogenation. This study offers valuable insights into the design of photothermal catalysts, highlighting the significant potential of active-site engineering in promoting efficient CO₂ conversion for practical solar-to-fuel production.</p>