A high-performance catalyst, NF@0.1%Ni@CeO₂-V₀, was developed for concentrated solar-driven CO₂ reduction in H₂O vapor, achieving a CH₄ yield of 192.75 μmol/cm²/h with 100% selectivity and 1.14% solar-to-chemical efficiency. The catalyst features single-atom Ni anchored on oxygen vacancies (V₀) in CeO₂, enhancing H₂O dissociation and CO₂ reduction. The V₀ sites facilitate charge and phonon capture, promoting efficient H₂O activation. The high photon flux reduces the activation energy for CH₄ production and prevents V₀ depletion. The catalyst's structure, characterized by porous nanorods and single-atom Ni, enables efficient charge carrier trapping and thermal-photonic coupling. The study reveals that the combination of V₀ and single-atom Ni enhances charge separation, reduces recombination, and improves catalytic efficiency. Under concentrated solar irradiation, the catalyst achieves high thermal stability and reusability, with minimal degradation after six cycles. The mechanism involves thermal and photo-assisted H₂O dissociation, leading to CO₂ reduction to CH₄. The results highlight the importance of surface atomic structures in catalytic efficiency and provide insights for developing efficient solar-to-chemical technologies.A high-performance catalyst, NF@0.1%Ni@CeO₂-V₀, was developed for concentrated solar-driven CO₂ reduction in H₂O vapor, achieving a CH₄ yield of 192.75 μmol/cm²/h with 100% selectivity and 1.14% solar-to-chemical efficiency. The catalyst features single-atom Ni anchored on oxygen vacancies (V₀) in CeO₂, enhancing H₂O dissociation and CO₂ reduction. The V₀ sites facilitate charge and phonon capture, promoting efficient H₂O activation. The high photon flux reduces the activation energy for CH₄ production and prevents V₀ depletion. The catalyst's structure, characterized by porous nanorods and single-atom Ni, enables efficient charge carrier trapping and thermal-photonic coupling. The study reveals that the combination of V₀ and single-atom Ni enhances charge separation, reduces recombination, and improves catalytic efficiency. Under concentrated solar irradiation, the catalyst achieves high thermal stability and reusability, with minimal degradation after six cycles. The mechanism involves thermal and photo-assisted H₂O dissociation, leading to CO₂ reduction to CH₄. The results highlight the importance of surface atomic structures in catalytic efficiency and provide insights for developing efficient solar-to-chemical technologies.