This study presents a highly efficient nanostructured Ru/MnOx catalyst for photo-thermal catalytic CO2 hydrogenation to methane (CH4). The catalyst, composed of well-defined Ru/MnO/Mn3O4, achieves a remarkable CO2 conversion of 66.8% with a selectivity of 99.5% and a CH4 production rate of 166.7 mmol g−1 h−1 under mild conditions of 200°C. The synergy between photon energy and thermal energy reduces the activation energy of the reaction and promotes the formation of the key intermediate COOH* species. Spectroscopic and theoretical investigations reveal that the structural evolution of Ru/MnOx into Ru/MnO/Mn3O4 is facilitated by Ru-mediated H-spillover, enhancing catalytic activity. The catalyst demonstrates excellent stability and performance in both batch and fixed-bed reactors, with a high space-time yield of 95.8 mmol CH4 g−1 h−1. The study highlights the potential of photo-thermal catalysis for efficient CO2 hydrogenation to methane, offering a new strategy for sustainable carbon utilization. The results demonstrate that the combination of external heating and irradiation significantly enhances the reaction efficiency, making the catalyst a promising candidate for practical applications in carbon capture and utilization.This study presents a highly efficient nanostructured Ru/MnOx catalyst for photo-thermal catalytic CO2 hydrogenation to methane (CH4). The catalyst, composed of well-defined Ru/MnO/Mn3O4, achieves a remarkable CO2 conversion of 66.8% with a selectivity of 99.5% and a CH4 production rate of 166.7 mmol g−1 h−1 under mild conditions of 200°C. The synergy between photon energy and thermal energy reduces the activation energy of the reaction and promotes the formation of the key intermediate COOH* species. Spectroscopic and theoretical investigations reveal that the structural evolution of Ru/MnOx into Ru/MnO/Mn3O4 is facilitated by Ru-mediated H-spillover, enhancing catalytic activity. The catalyst demonstrates excellent stability and performance in both batch and fixed-bed reactors, with a high space-time yield of 95.8 mmol CH4 g−1 h−1. The study highlights the potential of photo-thermal catalysis for efficient CO2 hydrogenation to methane, offering a new strategy for sustainable carbon utilization. The results demonstrate that the combination of external heating and irradiation significantly enhances the reaction efficiency, making the catalyst a promising candidate for practical applications in carbon capture and utilization.