This study reports an efficient nanostructured Ru/MnOₓ catalyst for photo-thermal catalytic CO₂ hydrogenation to CH₄, achieving a significant production rate of 166.7 mmol g⁻¹ h⁻¹ at 200 °C with a superior selectivity of 99.5% and a CO₂ conversion of 66.8%. The catalyst, composed of well-defined Ru/MnO/Mn₃O₄, combines external heating and irradiation to enhance the reaction. Spectroscopic and theoretical investigations reveal that the yield of CH₄ is enhanced by coordinating photon energy with thermal energy, reducing the activation energy and promoting the formation of key intermediate COOH⁺ species. This work opens a new strategy for CO₂ hydrogenation toward CH₄, offering a promising route for addressing energy crisis and climate change.This study reports an efficient nanostructured Ru/MnOₓ catalyst for photo-thermal catalytic CO₂ hydrogenation to CH₄, achieving a significant production rate of 166.7 mmol g⁻¹ h⁻¹ at 200 °C with a superior selectivity of 99.5% and a CO₂ conversion of 66.8%. The catalyst, composed of well-defined Ru/MnO/Mn₃O₄, combines external heating and irradiation to enhance the reaction. Spectroscopic and theoretical investigations reveal that the yield of CH₄ is enhanced by coordinating photon energy with thermal energy, reducing the activation energy and promoting the formation of key intermediate COOH⁺ species. This work opens a new strategy for CO₂ hydrogenation toward CH₄, offering a promising route for addressing energy crisis and climate change.