This study reports a high-performance catalyst, NF@0.1%Ni@CeO2-Vo, for concentrated solar-driven CO₂ reduction to CH₄. The catalyst is synthesized by anchoring single-atom Ni around oxygen vacancies (Vₒ) on CeO₂ nanorods. Under concentrated solar irradiation, the catalyst exhibits a CH₄ yield of 192.75 μmol/cm²/h, a solar-to-chemical efficiency of 1.14%, and a selectivity of ~100%. The high photon flux reduces the activation energy for CH₄ production and prevents Vₒ depletion. The defects coordinated with single-atom Ni promote charge capture and local phonon generation, enhancing H₂O activation. Mechanistic insights reveal that Vₒ regeneration ensures a steady supply of active sites, while the hybridized molecular orbitals of H₂O and Ni, along with structural changes induced by Vₒ, enhance charge carrier trapping and reactant activation. Computational and spectroscopic studies confirm thermal and photo-dissociation of H₂O on the catalyst surface. This research provides valuable insights for developing efficient systems for direct solar-to-chemical energy conversion and designing catalysts for CO₂ conversion under concentrated solar irradiation.This study reports a high-performance catalyst, NF@0.1%Ni@CeO2-Vo, for concentrated solar-driven CO₂ reduction to CH₄. The catalyst is synthesized by anchoring single-atom Ni around oxygen vacancies (Vₒ) on CeO₂ nanorods. Under concentrated solar irradiation, the catalyst exhibits a CH₄ yield of 192.75 μmol/cm²/h, a solar-to-chemical efficiency of 1.14%, and a selectivity of ~100%. The high photon flux reduces the activation energy for CH₄ production and prevents Vₒ depletion. The defects coordinated with single-atom Ni promote charge capture and local phonon generation, enhancing H₂O activation. Mechanistic insights reveal that Vₒ regeneration ensures a steady supply of active sites, while the hybridized molecular orbitals of H₂O and Ni, along with structural changes induced by Vₒ, enhance charge carrier trapping and reactant activation. Computational and spectroscopic studies confirm thermal and photo-dissociation of H₂O on the catalyst surface. This research provides valuable insights for developing efficient systems for direct solar-to-chemical energy conversion and designing catalysts for CO₂ conversion under concentrated solar irradiation.