<p>Photothermal catalytic CO₂ hydrogenation is an effective means of utilizing carbon resources. However, it is severely limited in terms of kinetics and thermodynamics. Therefore, it is necessary to meticulously design catalysts to solve this problem. Herein, a sandwich structured NiO@InNi/In₂O₃ is designed to intrinsically regulate the direction of photogenerated carriers transfer, resulting in a CO yield of 42.97 mmol g⁻¹ h⁻¹ (1290.3 µmol h⁻¹) with a selectivity near to 100%. InNi alloy favors the collection of photogenerated carriers by the parallel way and enhancement of the adsorption and activation of CO₂ molecules. NiO grown on the surface of InNi alloy not only improves the adsorption of H₂ and provides sufficient H⁺ for the reaction, but also makes InNi alloy more stable during the reaction process. The photothermal effect caused by In₂O₃ accelerates the transfer of photogenerated carriers and increases the surface temperature of the catalyst, thereby synergistically promoting the reaction from a kinetic perspective. This work ameliorates the kinetic and thermodynamic limitations of the photothermal catalytic CO₂ hydrogenation process through rationally designing the electron transfer direction of the sandwich structured catalysts to parallel way.</p>